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By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart's model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison's case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison's classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

By W. R. Ingalls

THE propaganda in favor of the adoption of the metric system of weights and measures in the United States is founded upon the idea of compulsory adoption. There can be no argument about this, for the metric system has been legal, by Act of Congress, in the United States since 1866. Nobody ought to oppose an educational movement, and if pro-metric activities were confined to that there might be no reason to gainsay them. I do not propose to enter into any discussion of 'the relative merits of the metric and the English systems of weights and measures. The simple case is that the metric system not having made much headway in the United States after more than 50 years of legality, 'it is now aimed to force it upon the people by legislative compulsion. The main arguments in favor of such compulsory adoption are that it would- simplify the education of our children and would promote our foreign trade, for the reason that more countries of the world, with which we do business, use the metric system than the English system. I am going to disregard,' in this contribution, the first of these arguments, for it is largely conjectural." Not so with the other, which is specific, and being so its speciousness can be, proved. It is true that the metric system is used by more countries of the world than the, English system. It is commonly stated that of the Indo-European nations only the United States, Great Britain, and her colonies, and Russia have failed to adopt it. However, if with "colonies" we equate Canada, Australia, New Zealand, Tasmania and South Africa, we have a longer list of non-metric countries, and it comprises not only the most populous, but also the most industrial nations of the world.

Jan 1, 1921

By F. F. Sharpless

IT IS to be. read in Western newspapers that Hon. S. S. Arentz who introduced H. R. 7736, 'has repudiated it, that certain mining men in Utah and Nevada say that they will fight it "until hell freezes over." It is to be read in more temperate expressions that "the eminent engineers who drafted the bill exhibited a woeful misunderstanding of Western sentiment and opinion." Furthermore, it is averred that there is no need for revising the mining laws, that we have got along pretty well under the existing laws, etc. Such statements are so surprising in view of, the facts of record that it is hard to believe that the oppon-ents of the bill, who make them, are well informed, or that they represent general opinion. It will be useful therefore to review the record of the case. Our GOOD OLD MINING LAWS We have indeed got on well in our mining industry, but that has not been by virtue; of our good old mining laws. Rather has it been in spite of them. Ever since the Richmond-Eureka case in the '70s there has been litigation arising from them. Early in the '80s the apex law was discarded by common consent in Leadville, and it has been ignored in every district of flat-lying ore deposits ever since. The great mines of the present time are the porphyry copper deposits. At Bingham, Ely, Ray, Chino, Miami, Clifton and Ajo the apex law is simply inapplicable. A law that is inapplicable to the modern conditions of mining may be an old law, but it can not properly be characterized as a "good" law. For such reasons, and many others of weight, there has been a demand for revision of the mining laws; dat-ing ,back at least three decades. President Roosevelt appointed a commission to advise respecting the question, said commission comprising. Dr. James Douglas (chairman), John Hays Hammond, D: M. Barringer, Walter B: Devereux, and William B. Mather. This committee was unanimous on the following points:

Jan 1, 1922

By Prof John E. Church

ONE of the most striking phenomena connected with the mines on the Comstock lode is the extreme heat encountered in the lower levels. This heat is not due to the burning of candles, heat of the men, and decomposition of timbers, all intensified by bad ventilation, as was the case nearer the surface. It proceeds from the rock, which maintains constantly a temperature very much higher than the average of the atmosphere in Nevada. The heat of these mines is a matter of more than usual interest, for they are the only hot ones now worked in the United States, and both in the present temperature encountered and in the increase which is to be expected as greater depths are reached, they appear to surpass any foreign mines of which we have a record. Hot mines are known also in other countries, as in the tin and copper lodes of Wales, where one of the veins worked by the United Mines is known as the hot lode. It has springs which discharge water at a temperature of 116' Fahrenheit, the depth being 220 fathoms, or 1320 feet. The heat of the air in these workings is. given at 100' to 113' Fahrenheit. The air is bad, and the heat in the drifts seems to be traceable to defective ventilation rather than to the real necessities of the case. Air is supplied through a small pipe, and is drawn from a place where the temperature is 95' Fahrenheit. Under such circumstances it is not surprising to read that in this hot mine the air is hotter than the rock, a state of things which I hare never observed in the Comstock. Other mines have been reported to the British Coal Committee as having temperatures of 106" Fahrenheit and thereabouts, but the only positive comparisons that are available at this writing are the following, all from Cornish mines : Mine. Depth Temperature. in feet. Air. Rock. Tresaveau,.....1581 86° 83° to 85° Consolidated Mines,. .. 1500 87° 86° " " . 1722 94o 93° " L .. .. 1764 94o to 96° 921/2° to 931/2°

Jan 1, 1879

By N. H. Fisher

Geographical Distribution 'he most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig I). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation Ltd., of Melbourne, on Stradbroke Island, and in other places. Physiography Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 56 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, upto 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1949

By Leo Horvitz

Microanalysis of near-surface soils for hydrocarbons is the basis of a method for locating gas and oil deposits. To substantiate this technique, evidence of vertical migration of hydrocarbons from petroleum accumulations is presented. Tabulated data relevant to hydrocarbon surveys conducted in several petroleum provinces are included. PEROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer' in Germany and by Sokolov in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas. Since 1936 work on petroleum exploration techniques of this type has been going on in this country. However, instead of determining hydrocarbon content of soil air collected in the field, investigators analyze samples of the soil itself for adsorbed and occluded hydrocarbons, which are released by suitable treatment and found in larger amounts than are the quantities reported for soil air. Difficulties often encountered in collecting gas samples in the field, moreover, are eliminated when soil is used as the sampling medium. Field Procedure: Sample locations are first surveyed over the area to be investigated. Care is taken to locate the stations at considerable distances from roads, pipelines, drilling wells, and other sources of contamination. The borehole pay be dug with a bucket-type hand auger or with mechanical drilling equipment. Lubricants are avoided in either case. When the desired depth is reached, a sample is brought to the surface, placed in a pint glass jar or can, and securely sealed. Sample containers are carefully labeled and delivered to the analytical laboratory. Generally a satisfactory sampling depth range is 8 to 12 ft. In some regions, however, satisfactory data are obtained from samples collected at much shallower depths. Such is the case, for example, in areas of west Texas where the limestone and caliche near the surface occlude hydrocarbons and prevent their rapid escape to the atmosphere. In carrying out broad reconnaissance surveys in search of large features, considerable time is saved by first taking samples one-fourth to one-half mile apart along profiles about one mile apart. If the analytical data indicate a hydrocarbon anomaly of interest, additional samples are taken to produce a more dense and uniform sampling pattern within the interesting area. This sampling program is particularly adaptable to areas that are sectionized. In areas covered with a network of roads, sampling along these roads facilitates the reconnaissance survey. Actual sampling density used depends upon areal extent of features expected. When flanks of piercement-type domes where accumulations may be only several hundred feet wide are sampled, stations are often no more than 200 ft apart. Analytical Technique: Of the hydrocarbons composing petroleum, only the more volatile would be expected to reach the surface of the earth. The analytical technique, therefore, was developed to determine only those constituents that exert a vapor pressure at room temperature. Actually, in near-surface soils, only a very small part of the hydrocarbons are heavier than pentane. Details of the analytical technique have previously been reported. Only a brief description of the methods will be presented here. A weighed portion of the sample, about 100 g, is first treated with an aqueous solution of copper sulphate and then with phosphoric acid in a partial vacuum. The copper sulphate prevents the reaction of the acid with carbides that may be present because the sample has been contaminated by auger particles. Such a reaction may produce spurious methane. The role of the acid is to decompose any carbonates present, thereby helping to release the hydrocarbons. The carbon dioxide is removed with potassium hydroxide and the flask containing the

Jan 1, 1955

By Edward W. Parker

One of the most important features of the coal-mining industry of the present day is one that is common to the majority of industrial enterprises—the substitution of mechanical methods for hand-labor.

Jan 1, 1900

By Paul D. Foote

Most of the treatises on metallurgy intimate that simultaneously with the development by the atomic physicist of a really satisfactory theory of the atom will be inaugurated a new epoch in the science of metals. Metallurgically and metaphorically, we shall dwell in the Utopia of Sir Thomas More. It is my privilege this afternoon to demonstrate that this state has not arrived. An atom is a miniature planetary system consisting of a positively charged nuclear sun about which revolve electrons each carrying the negative charge e. The charge on the nucleus is + Ze where Z is the atomic number and the number of planetary electrons in a neutral atom is equal to Z. These electrons are arranged in several groups having different binding energies. Ordinary x-ray phenomena relate to processes occurring deep within the atom, usually with electrons in the so-called K or L shells. Such electrons in the heavier atoms are so closely bound to the nucleus that the forces exerted by neighboring atoms in a solid are relatively inappreciable. For most practical x-ray investigation, the atom may be considered as in the gaseous phase completely isolated from its neighbors. The K radiation from an element in the gaseous state, in the solid or liquid phase, or even in combination with other elements in all its possible valences, is almost identical.‡ Visual and ultraviolet spectroscopy is concerned with disturbances of the most loosely bound outer or valence electrons of the atom, always in the vapor state. The remarkable progress of the last year in both theo-

Jan 1, 1926

By Lyman Taylor, Alexander R. Troiano

STUDIES of the transformation of austenite at constant subcritical temperatures have been numerous since the work of Davenport and Bain.1 Considerable information has been obtained on low-alloy steels and on high-carbon alloys containing undissolved carbide or graphite at the austenitizing temperature. Little is known of the isothermal transformation of austenite containing in solution large amounts of both carbon and a single alloying element. In this investigation four steels containing one per cent carbon and with chromium in the range 3 to 9 per cent have been examined with the view to establishing the fundamental character of the isothermal reactions when all carbon and chromium are initially in solution in austenite. EXPERIMENTAL PROCEDURE Alloys The chemical compositions of the steels investigated are given in Table I. The 4 per cent Cr alloy is a commercial steel. The other steels were made by the Carpenter Steel Co. as 50-lb., induction-furnace heats and rolled to 5/8-in. round bars. Bars were softened at 650° to 700°C. before the specimens were cut. [ ] Metallographic Method Most of the lines on the transformation diagrams presented here have been placed on the basis of the microscopic examination of partially reacted specimens. Thees specimens were approximately ½ by ¼ by 1/8 in. in size. Specimens of the 9 per cent Cr steel were held 10 to 12 hr. at 1200° to I225°C. before quenching to the various subcritical temperatures. The other steels were held for 2 to 2 ½ hr. at 1200°C. before quenching. These treatments, carried out in an atmosphere of purified nitrogen, produced an austenite grain size larger than A.S.T.M. No. I, some grains being 1 to 2 mm. in diameter. There were a few undissolved carbide particles in some specimens of the 9 per cent Cr steel. It is believed, however, that any errors in the results due to incomplete solution of carbon and chromium in austenite are negligible; that is, austenite compositions may be considered as being those listed in Table I. X-ray Methods Constituents were identified and martensite axial ratios determined from Debye

Jan 1, 1945

By Thomas T., Read

THE education of adolescents to perform the duties and assume the responsibilities of maturity has been a characteristic of human society since the dawn of history. In the beginning the members of the immediate family performed this function, and in modern life they still have an important part in it. Possibly religion was the first field in which education began to be functional; young people were sent for instruction to a teacher who had a broader and deeper knowledge of the subject than was possessed by the family. It does not seem necessary for our purpose to attempt to determine how, when, or where instruction in the practical arts first' began to become functional, and the brief outline which follows must suffice. The discovery and utilization of mineral substances to improve and maintain the conditions of human living is a practical art, which must have had an almost accidental origin and have been developed by empirical experiments. We do not know, nor would it be useful to try to fancy, how men first learned that they could make use .of mineral substances to their benefit, but how- ever that knowledge was initially gained it was certainly trans mitted through instruction in the family. At first such activities must have been merely a .minor part of the making of a-living, but in time those who excelled found it better to devote them-

Jan 1, 1941

By F. E. Bash

CONSTANTAN is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported acid the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a, process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts. against pure iron at 1500° F. (816° C.) with the cold-junction temperature at 0° F., or a proportional e.m.f. at temperatures near 1500° F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure

Jan 9, 1919

By Bror Nordberg

SAND and gravel are unconsolidated granular materials resulting from the natural disintegration of rocks. The two materials nearly al- ways occur together, variably proportioned in widely available de- posits. A commercial sand comprises the fine granular material, usually less than f in. in diameter (ASTM Designation C58-28), and gravel consists of the coarse, granular material larger than sand (ASTM Designation C125-46T). Gravel falls within the range of 1/4 in. and a top size usually of 3 ½ in. Chemical definition is impossible. Sand and gravel are always of secondary origin. They were formed from various massive rocks through the action of chemical and mechanical forces; then transported, abraded, washed, sorted, and classified by streams, glaciers, waves, or winds, to be redeposited in beds as they are found. Chief disintegrating forces in the reduction of rocks into granular particles were frost, rain, the dissolving action of acid and alkaline ground waters, the mechanical action of streams and waves, and the action of glaciers. Method of formation and deposition have imparted physical properties to sands and gravels that largely determine the commercial value of the materials for particular use and influence the manner of exploitation. In the early days of the commercial industry, purchasing specifications were relatively lenient but in. the past decade much more rigid quality requirements have had to be met for acceptance by all classes of purchasers. The trend to further severity in requirements is a challenge to the industry that commands full knowledge of the nature of raw materials at hand and skillful application of processing into commercial products. Mechanical strength, the ability to resist disintegration, chemica

Jan 1, 1949

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By John V. Beall

STREAM pollution caused by waste waters from mineral industry operations is a problem that has grown up with the industry. Its importance to each operator is dependent on the amount and type of waste he dumps into the rivers and streams; on whether this waste pollutes the waters sufficiently to make them unfit for potable water, irrigation, and conservation of wild life; and on whether this waste makes a safety or health hazard. Through the years our growing population and industry have made increasing demands on the mineral industries, the suppliers of the raw materials on which our industries are based; and we have met these demands at some sacrifice to the natural beauty and cleanliness of our country. However, that is often the unavoidable nature of the business, and along with the increased use of our

Jan 1, 1948

By J. C. Bayles

Jan 1, 1886

By Wheeler Davey

WHEN metals are subjected to mechanical working, such as rolling, one of the phenomena that take place is a movement of the crystals of the metal into a system or systems of orientation which bear an angular relation to the direction of working. In rolled metal the crystals may orient themselves with respect to the rolling plane or the rolling direction, or both. Direct evidence of the existence of preferred orientations in rolled metal has been obtained by numerous investigators from X-ray patterns of the rolled metal. Most of these workers used a monochromatic pinhole method. Where the degree of preference for a single orientation is high the monochromatic pinhole pattern may be interpreted by a geometrical calculation based on the angular relationships of the planes in the crystal and the diffraction arcs on the X-ray pattern. This process may be aided by the geometrical construction of the locus sphere (Langenkugel), and reflection circles of Polanyi,1 Polanyi and Weissenberg,2 and Mark and Weissenberg,3 and of the plane polar figures (flachenpolfigur) of Franz Wever.4 R. M. Bozorth5 solves X-ray patterns from metals having a single preferred orientation by means of a series of charts which when placed over the X-ray pattern give directly certain angular relationships, between the crystal planes and the surface of the specimen.

Jan 1, 1929

By O. H. Eschholz

The electrostatic process of fume precipitation is an excellent example of the successful application of scientific knowledge to an industrial operation. Originally proposed for the precipitation of sulfuric acid mists, it has been extended until at present there is practically no fume-carrying gas to which the method cannot be applied. Among the more common applications are: the recovery of non-ferrous smelter flue-dust, iron blast-furnace dust, cement dust, and potash fume. It should be borne in mind that the process is restricted to the precipitation of suspended particles, either liquid or solid, and does not separate gaseous constituents. However, by proper temperature control, mixtures of vapors having different temperatures of condensation to either solids or liquids may be selectively precipitated. The process consists essentially of subjecting suspended particles, including those too minute to be effectively acted upon by centrifugal or gravitational forces, to such an electrical force that they are driven from the gas stream, acting as a conveyer, and deposited upon a suitable receiving surface. This directional impulse is obtained from the interaction of charged particles and an electrostatic field of definite intensity gradient existing between two dissimilar electrodes, known as discharge and receiving electrodes. In principle, the equipment is equally simple. As shown diagrammatically in Fig. 1, it consists of: (1) A source of high-potential direct, current,, requiring: (a) Source of alternating-current energy. (b) Means of transforming from low voltage to high voltage. (c) Means of converting alternating to direct current. (2) Precipitation chamber having: (a) Transmission tubes for fume-laden gases. (b) Suitably designed and disposed electrodes. (c) Means for affecting removal of deposited solids. Although Hohlfeld demonstrated, in 1824, that a smoke-laden atmosphere could be cleared by applying an electrostatic field, and while Sir

Jan 1, 1919

[SWEETSER, R. H.: Discussions: on Evaluation of Coal for Blast furnace Coke, 94, 378, 394,385 on Mt. Union Sand Flotation Plant for Preparing Bituminous Coal, 74, 591 on Need for Research in Foundry Pig Iron, 76, 450 on Pig Iron Low in Total Carbon, Is in Demand for Use in Various Industries 75,471 on Properties of Coal Which Affect Its Use in the Ceramic Industry, 101, 254 on Relation of Ash Composition to the Uses of Coal, 74, 471 on Research on Blastfurnace Slags 100, 137.138 on Selection of Coals for the Manufacture of Coke, 74, 637 on Sinter in Blast-furnace Burdens, 100, 54 on Sintering Limonitic Iron Ores at Ironton, Minnesota, 90, 355, 356 on Slag Control in the Making of Iron and Steel, 116, 104, 115, 116 on Solubility of Nitrogen in Liquid Iron, 116, 193, 194 on A Statistical Analysis of Blast-furnace Data, 96, 70]

Jan 1, 1936

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957