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By W. S. Gillam

A need for new supplies of fresh water exists today and in many specific areas that need is urgent. One solution lies in saline water conversion, a problem complicated by cost factors. The principles involved in saline water conversion, the status of development, and the estimated costs (present and future) of several processes are presented. Among the methods discussed are distillation, electrodialysis, and freezing. In general, the costs presented are based on a standardized procedure for estimating conversion costs, permitting a valid comparison among the various processes. The need for new supplies of fresh water and the potential benefits to be derived from an abundant supply of converted water are recognized by practically everyone concerned with water problems. The water supply problem exists today; it is urgent in many specific areas in this country and also in the world, and it will become more acute in the future. One answer to the growing problem of adequate water supplies is the development of new sources. Very significant quantities of brackish underground and surface waters exist in certain areas and an inexhaustible supply of ocean water is available. Thus in many areas water resources can be extended through saline water conversion. Congress recognized the need for new sources of fresh water in 1952 and passed the Saline Water Act, Public Law 448, amended it in 1955, and in September 1958, enacted Public Law 85-883, calling for the construction of at least five demonstration plants. The program is administered by the Dept. of Interior through the Office of Saline Water, and its primary objective is to reduce the cost of converted water produced, whether it be by development of new processes or improvement of known processes. This is a most difficult problem and one that will require several years of prodigious effort. It is difficult—not because of any intricate or new chemistry, engineering, or physics involved—but because of the difficulty in converting water at low cost. Whatever the sources of the saline water, the salts which are held tenaciously in solution must be removed before the water becomes suitable for industrial or domestic uses. Saline water is a relatively simple system of salts dissolved in water. It has certain chemical and physical properties that determine the various methods by which the salts may be separated from the water. The system, although not complex, in most instances, has had countless years in which to reach equilibrium and is, therefore, comparatively stable. Because of its stability, separation of saline solutions requires relatively large quantities of energy. The unique properties of water depend on the fact that its molecules are chemically active. The chemical and physical properties of water are associated with the type of bonding involved in the water molecule. Chemical changes such as hydrolysis, or rusting of iron, involve the breaking of chemical bonds between the hydrogen and oxygen atoms. Physical changes, such as evaporation in a boiler, the melting of ice, or the viscous resistance to flow in a pipe, involve breaking of the hydrogen bonds. (The hydrogen nucleus is so small that it can attract two negative atoms.) Thus water molecules not only combine with molecules of other compounds but even with one another; e.g., each molecule may be bounded to four other molecules. Water molecules cling to the ions of dissolved salt to form water-encumbered hydrated ions and they cling to one another to form entangling networks through which hydrated ions can be propelled only by tearing the networks apart. That is one reason why considerable energy still needs to be expended in our simplest procedures for purifying water. If water molecules did not have this habit of clinging so tenaciously to other molecules, and to one another, it would be easy to push salt ions past the water molecule and get a separation. But the water would not then dissolve salt, so the problem would not exist.' Water when heated evaporates very slowly, relative to other liquids having simple molecules. Vaporization involves the separation of molecules from the liquid, and this means overcoming the attraction between molecules which is due to the hydrogen bonding. The heat of vaporization for water is high; consequently, the boiling point of water is also high. Water boils at 100" C; hydrogen sulfide (H2S) at -60" C; oxygen (02) at -183" C; nitrogen (N2) at -196" C; and methane (CH4) at-161°C, even though the latter has about the same molecular weight as water. Because of these peculiar properties of water, it exists as a liquid on earth instead of a gas such as hydrogen sulfide or nitrogen and oxygen.

Jan 1, 1961

By James Fiore

The Nuclear Waste Policy Act of 1982 provides a set of rules for proceeding with the identification and selection of sites for a mined geologic repository as well as for interim storage facilities for high level waste in the event storage facilities are needed. The following paper summarizes the sequence of procedures in site selection, and presents the interaction of governmental agencies, the states, the public, and affected Indian tribes in this process. Several agencies have published regulations assocated with the selection of high level waste sites. These regulations set down a diverse collection of requirements designed to ensure public safety. This paper identifies the organizations working to satisfy these requirements, and outlines the role of the geotechnical community in performing data collection activities to support these same requirements.

Jan 1, 1984

By Jeffrey W. Nelson

Predictions of creep closure for periods ranging up to more than 1,000 years are needed for designing a radioactive waste repository in a salt formation. Such long-term predictions must be based on the use of laboratory and field test results extrapolated by numerical modeling. Laboratory test results are presented which show highly variable creep behavior for salts from different sites as well as salts from the same site. Comparisons of measured creep closures against predicted closures are presented for two deep boreholes in Louisiana salt domes and for an exploratory shaft and drift in southeastern New Mexico bedded salt (WIPP). These data illustrate the significant uncertainties involved in long-term closure predictions and indicate the critical need for site-specific, in situ closure measurements over extended periods of time for repository design.

Jan 1, 1984

By Mark Eisner

ONE'S JOB is the watershed down which the rest of one's life tends to flow write the Lynds in the first pages of their classic social study, "Middletown in Transition." Certainly engineers will confirm this statement after a check among those in their own profession with whose lives they are at all familiar. I have no hesitancy in acknowledging the truth of their observation for the men and women who are engaged in the profession of the law. It has been often remarked that American public life is overrun with members of the law profession. The highest public office in the land, that of President. has been occupied by lawyers almost to the exclusion of citizens of any of the other professions. Twenty-two Presidents of the United States out of the total of 31, were members of the bar. For the most part, members of Congress, the governors of the states, the state legislators and the mayors and other local leaders, men who occupy important positions of responsibility and public trust, have had legal training. Now this fact is no mere accident. Those who were fitted for the "job" of the practice of the law are favorably placed with respect to their participation in public life. Thus public service and public office is the watershed down which the "lawyer's" life tends to flow.

Jan 1, 1940

By E. H. Dix

All commercial aluminum contains small percentages of copper, iron, and silicon as unavoidable impurities. The purest metal obtainable commercially, special grade high purity ingot, contains a maximum of 0.50 per cent. impurities of which the usual minimum amount of copper is 0.01 per cent.; silicon, 0.12 per cent.; and iron, 0.20 per cent. This grade is too costly for most purposes. The two standard grades, Nos. 1 and 2, containing a minimum of 99.0 and 98.0 per cent. aluminum, respectively, are more generally used. Other grades of secondary aluminum often contain as high as 3 or 4 per cent. of impurities, which include 1 per cent., or more, of zinc. Specifications for high-grade aluminum-casting alloys generally allow a maximum of 1.7 per cent. for total impurities. The S. A. E. Specification No. 33, which is intended to cover alloys made from secondary aluminum ingot, gives the iron maximum as 1.5 per cent. and the maximum for silicon (including manganese and tin) as 0.75 per cent. The effect of even relatively small amounts of impurities on the physical properties of ingot aluminum is shown by the following cornparison of two lots of aluminum, which may be taken as representative of special grade and grade No. 2 ingot, respectively. AnalysEs Special Grade, Gbade No. 2, Per Cent. PeR CBnt. Copper................................. 0.01 0.32 Silicon................................. 0.12 0.32 Iron................................... 0.42 0.82 Aluminum.............................. 99.45 98.54

Jan 1, 1923

By E. H. Dix

All commercial aluminum contains small percentages of copper, iron, and silicon as unavoidable impurities. The purest metal obtainable commercially, special grade high purity ingot, contains a maximum of 0.50 per cent. impurities of which the usual minimum amount of copper is 0.01 per cent.; silicon, 0.12 per cent.; and iron, 0.20 per cent. This grade is too costly for most purposes. The two standard grades, Nos. 1 and 2, containing a minimum of 99.0 and 98.0 per cent. aluminum, respectively, are more generally used. Other grades of secondary aluminum often contain as high as 3 or 4 per cent. of impurities, which include 1 per cent., or more, of zinc. Specifications for high-grade aluminum-casting alloys generally allow a maximum of 1.7 per cent. for total impurities. The S. A. E. Specification No. 33, which is intended to cover alloys made from secondary aluminum ingot, gives the iron maximum as 1.5 per cent. and the maximum for silicon (including manganese and tin) as 0.75 per cent. The effect of even relatively small amounts of impurities on the physical properties of ingot aluminum is shown by the following cornparison of two lots of aluminum, which may be taken as representative of special grade and grade No. 2 ingot, respectively. AnalysEs Special Grade, Gbade No. 2, Per Cent. PeR CBnt. Copper................................. 0.01 0.32 Silicon................................. 0.12 0.32 Iron................................... 0.42 0.82 Aluminum.............................. 99.45 98.54

Jan 1, 1923

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers' mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby's two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951

By J. R. Finlay

The Cæur d'Alene silver-lead mining district of northern Idaho is probably best known to the general public as a seat of labor-troubles. So far as the writer is aware, little has been written and little is known about its geology and resources. People interested in lead-smelting are, of course, cognizant of the economic importance of the region, but they have not communicated much of their knowledge to the public. Exact figures as to the total output of the district are not obtainable, but the following estimates, covering the entire output of the 15 years during which the mines have been operated, are believed to be approximately correct: Group of Mines. Product. Wardner Group, including the Bunker Hill and Sul livan, Empire State-Idaho, Last Chance, Sierra Nevada, bur d'Alene Development Co... . $17,500,000 Cafion Creek Group, including the Gem, Frisco Con solidated, Granite, Standard, Mammoth, Hecla, Tiger-Poorman, Custer and Bell,.... 35,000,000 Mullan Group, including the Morning, You Like and Gold Hunter,........7,500,000 $60,000,000 This output covers the period of discovery and early struggles, and several periods of stagnation caused by strikes and other serious labor-troubles. In 1900 the output of the district was fully $10,000,000, and this figure would have been considerably increased in 1901 had not a curtailment of production been forced by the condition of the lead-market. In 1901 the product was about 150,000 tons of concentrates, with a gross. value of $8,250,000.

Jan 1, 1903

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By J. A. Cordier

USINOR has conducted four blast furnace tests with formcoke made from marginal coals in the pilot plant of HBNPC ("H. B. N." process) in four different blast furnaces of various sizes and with medium and high grade burdens. The tests in which up to 30% of the blast furnace fuel burden was replaced by HBN formcoke yielded good results on furnaces ranging in hearth diameters from 5.6 to 9.5 m. The tests demonstrated that: - the slight increase of pressure drop in the stack did not prevent smooth operation at record production rates with the same blowers - the total coke rate was not significantly affected, but there was a slight increase of the calorific value of the top gas - the hot properties of the formcoke are satisfactory as seen from the samples withdrawn at the tuyeres and tapholes. At the end of the two months test on BE nº 2 of Dunkerque, the hearth was as permeable and clean as with good standard coke. Our conclusion is that HBNPC formcoke made from lean coals is an adequate substitute for conventional coke in the range of 20 to 40% replacement, which is of interest to USINOR.

Jan 1, 1977

By J. E. Berg

THE geology of the Coeur d'Alene mining district is so familiar to every one interested in mining that I will only note as an introduction that the main producers are mines whose orebodies lie in the Revett or Burke quartzites ; that the known orebodies in the eastern part of the district all lie north of the Osburn fault; that the Prichard formation is quite generally looked upon as being unfavorable for lead deposits ; that the monzonite intrusive mass extending north from Gem to Sunset Peak, and over into Cedar Creek divide, is considered to have been the prime agent in the crea-tion of our orebodies, and that diabase dikes are a quite common feature at most of the properties with which I am familiar. Some of the exceptions to these statements may be mentioned. The Interstate-Callahan mine is considered the exception disproving the alleged relation between large ore-deposits and the Prichard formation, but this property was primarily a zinc producer, with lead secondary, though of sufficient tonnage to be a valuable product. A second interesting occurrence in the Prichard worth calling to your attention is the Jack Waite property, on Tributary Creek, north of Murray. This vein lies at a low horizon in the Prichard forma-tion, and the ore differs essentially from others in the same horizon elsewhere in that it is a clean, medium to coarsely crystalline, lead ore carrying very little zinc, about one ounce silver to ten units lead, and is accom-panied by a clean quartz gangue or vein filling. I believe that quartz was the primary mineral in the fissure, and that the lead ore was deposited in the vein as a replacement of the quartz.

Jan 7, 1927

Jan 1, 1971

By D. L. Feucht, R. L. Longini

The semiconductor heterojunction is considered in terms of simple models which may lead to an understanding of move complex heterojunctions. Metallurgical and electrical properties of hetero-junctions aye discussed including the interface structure, energy -band diagram, and carrier transbovt across the interface. It is found that in a heterojunction all mechanisms such as injection, tunneling, and junction recombination found in simple junctions play modified voles. INTERFACES between materials (grain boundaries, the electrical junction between two differently doped materials in a single crystal, the oxide-metal interface, or metal-metal junctions) are of considerable importance in many situations. These various interfaces all have one very fundamental thing in common. Quantum mechanically speaking, the wave functions of the electrons in one material may penetrate the other material but, in general, only to the extent of angstroms. From an electrical point of view the conduction mechanism changes as a current passes through such junctions. In some cases the change is tremendous, in others almost negligible. The interface, then, is the locus of a change of conduction mechanisms. Some of these, particularly in semiconductors, are well-understood. The ordinary p-n junction in a single crystal can be the locus of an injection mechanism or a tunneling process, depending on conditions. The mechanisms are probably best understood in semiconductors because of the possible simplified view of particlelike conduction. The bands are either nearly filled or nearly empty and band overlap is seldom involved. The same fundamentals are probably important in other situations too but they are very difficult to look at naively. Although the simple look at the semiconductor case only gives us a relatively rough picture which must then be refined, the other systems, which involve a more complex situation, immediately are in many ways too difficult. There are too many initial choices of complex systems and therefore it is not possible to be even reasonably certain of any one model. Because of the relative simplicity of semiconductors, their good and controllable structure, and because of the ability to make many measurements on them not normally available to either metals or insulators! they are probably the best understood materials. It is therefore desirable to use them as a tool to further the understanding of interfaces in general. Semiconductor-heterojunction concepts were first proposed by kroemer1 in 1957. This was followed several years later by reports on the fabrication and experimental characteristics of heterojunction structures by Anderson2 and Diedrich and jotten.3 I) THE HETEROJUNCTION STRUCTURE To get down to hardware, when we refer to a semiconductor heterojunction we imply that there exists an intimate contact between different semiconductor materials. We could put two pieces of material together, complete with oxide layers, we could remove the oxides, or we could even melt the interface and hopefully get wetting and a good "bond" on solidifying. In fact we could by some means grow a crystal of one material using the other as a seed. Essentially we are interested only in the last two because they are the simplest to look at analytically. The degree of perfection of fit varies greatly and is reflected somewhat in the arc welder's joint strength. The lattice match of the two materials, their orientation, and so forth. is obviously necessary for a good bond but so is the continuity of any polar bonds which are involved such as in the III-V semiconductors. The mechanical misfit between two similar lattices can be described in terms of edge dislocations. The edge-type dislocations must be very close together for the usual misfit and there must be dislocations for each of several different Burger's vectors in order to produce a lattice match. The .'dangling bonds'' resulting will be involved in producing interface charge. Order of magnitude estimates of the charge density extrapolated from low densities of dislocations in homogeneous materials give 5 x 1013 cm-2 Ge-Si and 1 X 1012 cm-2 Ge-GaAs electronic charges. Edge dislocations also act as very active recombination centers between holes and electrons. One lattice "matching" difficulty usually exists even if two structures have essentially the same lattice constants as they will have different coefficients of therma1 expansion. Thus, on cooling from the usually high temperature of fabrication to room temperature, dislocations are produced, a good fit not existing at both temperatures. In brittle materials this shrinkage may even result in cracking. For the Ge-Si interface the mismatch is about 2 x 10 -6 per degree whereas it is less than 10"7 per degree between germanium and GaAs. The exact effect of the misfit is dependent on the thickness of the materials involved. For a very

Jan 1, 1965

By H. E. Wheeler

The work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of the Ordnance Department, U. 8. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. Part I In the Haber process for the manufacture of ammonia from its elcnlents, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600' C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-stee1 forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 1, 1922

By H. E. Wheeler

The work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of the Ordnance Department, U. 8. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. Part I In the Haber process for the manufacture of ammonia from its elcnlents, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600' C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-stee1 forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 1, 1922

By Edgar Bain

SUMMARY THE results of an enquiry into the structural nature of some 70 iron alloys containing both nickel and chromium over a considerable range of concentration 'are briefly described in this paper. This study is a part of a comprehensive program of investigation into alloys involving chromium in progress at the Union Carbide and Carbon Research Laboratories. All the compositions studied contained carbon in amount comparable to commercial alloys.

Jan 3, 1927

By R. J. Lytle

Geophysical exploration for engineering purposes is conducted to decrease the risk in encountering site uncertainties. Such studies are needed in construction of underground facilities. Current responsibilities, opportunities and challenges for those with geophysical expertise are defined. These include: replacing the squiggly line format, developing verification sites for method evaluations, applying knowledge engineering and assuming responsibility for crucial national problems involving rock mechanics expertise.

Jan 1, 1982

By C. Ernest Birchenall, Robert F. Mehl

APPLICATION of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion coefficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner1 derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smiths on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 ACTIVITIES IN BRASS9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by azn = Pza/Pzn° [I]

Jan 1, 1947

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967

By John D. Kalasky, Stephen Krickovic

Adequate ventilation in coal mines depends upon good face control, as well as upon a well designed and properly controlled overall ventilation system. The fundamentals of effective bleeding for provision of good ventilation and control and removal of methane are described. The various mine pillaring systems for which it is both easy and difficult to provide effective bleeder systems are detailed. Bleeders in conjunction with longwall mining are also discussed.

Jan 1, 1974