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By L. W. Reynolds, R. F. Campbell, K. G. Carroll, S. H. Ballard

Based on metallographic and X-ray data probable equilibrium conditions from 1340" to 2400°F are presented for the composition range investigated. These are correlated with investigations of Takei and Kuo. Provision is made for existence of Mo, C and (Fe, Mo)2,C, carbides heretofore omitted in diagrams in this composition range. These carbides and (Fe, Mo),C, in equilibrium with ferrite and austenite, restrict the austenite and austenite + ferrite fields to lower carbon contents and higher temperatures than in the Fe-C system. OK groups of steel of different molybdenum content, but with approximately the same carbon variation in each group, Table I, were studied. The alloys were melted in an acid-lined 30-lb high-frequency induction furnace, and the ingots forged to l-in. rounds, which were then ground to 0.75-in. diam. To minimize chemical segregations a short length of each bar was given a high-temperature heat treatment as listed in Table I. Specimens 0.062 to 0.125-in. thick were thereafter cut from the homogenized bars for heat treatment to determine phase changes in the alloy. Heat treatments were performed in either a lead bath or muffle-type electric furnace, depending upon the temperature required. Maximum temperature variation was * 2" F in the lead bath and * 5"F up to 1900°F and +8"F above 1900°F in the electric furnace. Adequate protection of the specimen from the oxidizing atmosphere in the electric furnace was obtained by sealing the specimen in either a pyrex or a silica capsule which was evacuated or not as circumstances required. For austenitizing followed by quenching to an isothermal temperature, the specimen was placed in a closed-end refractory tube the mouth of which, extending beyond the furnace, was connected to a vacuum pump. The specimen could be withdrawn from this tube and quenched as desired. IDENTIFICATION OF PHASES The principal method of identification of phases was metallographic examination conducted on surfaces well removed from exposure to lead or atmosphere effects during heat treatment. Hardness measurements (Dph/lOkg) were also made on these surfaces. The etching reagents used and their effects are listed in Table II. Martensite and ferrite were readily recognized by their customary appearance after etching with saturated picral or 1 pct nital. The presence of liquid at high temperature was indicated by curved interfaces characteristic of boundaries between solid and melt, by intergranular pools of dendritic areas in a carbide matrix, and by a black network coincident with austenite grain boundaries. Examples of these structures are shown in Figs. l(a) and (0). The types of carbide which were attacked by the electrolytic chromic acid etch and the alkaline KMnO, etch, Table 11, were identified by X-ray analyses of extracted carbides of five alloys. Carbide residue was obtained from a metallographic specimen by etching the specimen for 24 hr in hydrochloric-picric acid in alcohol (grain-size reagent), after which the carbides, standing in relief, were scraped from the surface of the specimen and mounted on a glass slide. Diffraction patterns were obtained with a Philips spectrometer using iron-filtered cobalt radiation. Figs. 2, 3, 4, and 5 illustrate typical etching behaviors with chromic acid and alkaline KMnO,. Chromic acid attacked Mo,C as shown in Figs. 2(a) and (b)-but not (Fe, Mo),C, Fig. 3(b). Alkaline KMnO, attacked (Fe, Mo),C, Fig. 3(c), and also attacked M0,C. In accordance with these behaviors, a typical differentiation of coexisting Mo,C and (Fe, Mo),~ is shown in Figs. 4(a) and (b). The carbide (Fe, Mo),,C, could not be obtained free of other coexisting carbides for etching experiments. The behavior. however. of coexisting carbides identified by x-ray diffraction as Mo,C ind (Fe, Mo),,C, indicate that (Fe, Mo)23C6 is not etched by chromic

Jan 1, 1961

By D. J. Carney, J. Chipman, N. J. Grant

SINCE the beginning of this century it has been known that hydrogen contributes to the porosity of steel and that it is harmful to its mechanical properties. The evidence for this has been largely qualitative. Steel to which hydrogen was purposely added. in sufficient .amounts was shown to be either porous or brittle or both, whereas similar steel of low hydrogen content was shown to be free of porosity and to possess normal physical properties. There have been a considerable number of qualitative experiments of this type. Also, early in this century, a few attempts were made to measure the amount of hydrogen normally dissolved in commercial steels. This was usually done by placing the sample under an inverted liquid column such as mercury and collecting the evolved gas. These attempts, while not successful in measuring actual amounts of dissolved hydrogen gas, were able to prove that this gas will diffuse out of steel at room temperature, and that the amount of hydrogen dissolved is normally very small. On the basis of such qualitative evidence, hydrogen has been and still is blamed for a great number of the troubles encountered in the steel industry. In recent years, partial solutions for many steel-working problems have been obtained. These have led to increased interest in accurate quantitative work on hydrogen in steel, with the expectation that the results might possibly answer a few of the remaining unsolved problems. Commercially, two of the obvious questions which are in need of an answer are: (1) what are the most important sources of hydrogen, and (2) what quantity of hydrogen can be tolerated in various steels? There are many other unanswered questions. To begin to find the answers it seemed logical to start at the beginning of steel production with the liquid metal. Further, it seemed almost imperative to solve first the problems of analysis and sampling of the metal for hydrogen. Once these problems have been solved, it would be possible to answer more of the important commercial problems mentioned above. As a consequence, it was decided to design an analytical apparatus and, upon satisfactory completion of this, to develop an accurate method of sampling liquid metal for hydrogen.

Jan 1, 1951

By EDWARD B. DURHAH

The illustration Fig. 12, of the paper of Edward B. Durham, "Electrolytic Refining at the U. S. Mint, San Francisco, Cal.," printed in Bulletin No. 58, October, 1911, p. 830, contained an error. The corrected diagram is printed below.

Nov 1, 1911

By Richard T. Ely

Conservation, narrowly and strictly considered, means the preservation in unimpaired efficiency of the resources of the earth; or in a condition so nearly unimpaired as the nature of the case, or wise exhaustion, admits. And broadly considered, it means more than the word itself implies, for it naturally includes an examination of methods whereby the natural inheritance of the human race may be improved; and still more broadly considered—and as used in popular discussion—it includes a treatment of the effects of productive conservation measures upon distribution. We shall give our attention briefly to the main points in this informal definition before we pass on to the thesis that conservation is largely a matter of property relations—-that a wise conservation policy means wise property relations.

Jan 1, 1916

By AIME AIME

THE non-ferrous alloys have been placed in the same class with steel by metallurgical research on hardening, and hardenable alloys of all metals except zinc are now manufactured. The hardening of the non-ferrous alloys is accomplished by a process of heating, quenching and ageing. R. S. Dean, head of the research department of the Western Electric Co., told of the results of this research in 'a lecture on "Recent Advances in the Art and Science of Fabricating Metals," given before the Missouri Mining and Metallurgical Association on Jan. 24, 1929.

Jan 1, 1929

By George J. Young

The nature of slimes handled in the treatment of gold- and silver-ores has been discussed in technical literature to a considerable extent. The subject of slime-filtration from the practical worker's stand-point has also received much comment, arid scattered through the literature of the subject are descriptions of many slime-filtration installations. Articles of this nature serve a valuable purpose and assist materially in the design of new and the improvement of old plants. The subject of the physics of slime-filtration has been touched upon to only a slight extent. The underlying principles are worthy of niore intensive study and experimeritation than they have received, and the main purpose of this paper is to present the results of such study and experimental work as will serve to make clear in part at least many of the principles which control the filtration of slime. Nature of Slime. Much has been written concerning an accurate definition of the term "slime," but no comprehensive definition seems to be gcnerally accepted. The reason for this is clear. A slime consists of at least three different substances, each, when separated, possessing distinctly different physical and to a certain extent chemical properties. These substances are extremely fine sand, a colloidal material which may bc and generally is in a coagulated condition, and a colloidal material which is in a non-coagulated condition. Suspending a slime in a relatively large volume of water by shaking and allowing sedimentation to take place, results in the fine sand settling out with comparative rapidity, followed by the coagulated material, which settles niuch more slowly and finally a certain portion remains

Jan 1, 1912

By F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760° C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove.

Jan 1, 1932

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.' Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965

By J. D. Hanawalt, W. H. Gross

Magnesium has long been known as the lightest of our engineering metals. This metal, silvery white in color, has a specific gravity of only 1.74. Aluminum, the next lightest structural metal, is 1 ½ times heavier; zinc is 4 times heavier; iron and steel are 4 ½ times heavier; and copper and nickel are 5 times heavier. Magnesium does not occur in the free state but is very abundant in nature, constituting 2.5 pct of the earth's crust in the form of various ores. It is the third most abundant structural metal, being exceeded only by iron and aluminum. Magnesium is unique, however, in that in the form of magnesium chloride it also exists in the oceans. Sea water is the source most widely used for production in the United States but magnesium is also commercially produced from magnesite, dolomite, and other ores as well as from certain inland brines. The vast quantity of magnesium existing in the waters of the oceans can be visualized when it is realized that the removal of one hundred million tons per year (the approximate annual steel production in the United States) for a million years would reduce the magnesium content of sea water only from 0.13 to 0.12 pct, providing no more magnesium had washed into the sea in the meantime. Not only is magnesium potentially very abundant but it is in addition a very versatile metal and can be shaped and worked by practically all methods known to the art of metal working. It can be cast by sand, die, and the various permanent-mold methods;

Jan 1, 1953

By C. D. King

THE advances in basic open-hearth practice which have occurred during the past decade, have been principally in the direction of the physical development of larger units, decreased fuel consumption and increased length of furnace campaigns. However gratifying the economies which have resulted from these improvements are, it must be granted that like advances in chemical, physical-chemical and metallurgical knowledge pertaining to open-hearth practice would have added greatly to these already attained reductions in costs and it is the purpose of this paper to stimulate the discussion and study of these phases of cooperation and their relation to ingot yields. DEFINITION AND CALCULATION OF LOSSES In discussing basic open-hearth yields, the writer refers to the ingot yields obtained in the process of converting pig iron, scrap and ore to steel. In this conversion some scrap is produced. The difference between the total weight of ingots and scrap produced and the original metallic charge, constitutes the loss. Basic open-hearth yields vary considerably, and while some of the divergencies can be explained metal-lurgically because of differences in slag analysis, proportion of pig charges, and character of steel made, there often remain differences that apparently do not readily disclose themselves. In reconciling yields by the usual accepted methods of calculation, one is often forced to evaluate large losses as "unaccounted for." Such a system is prone to accept these large losses as inherent to the operation and not susceptible of appraisement and correction. It is obvious that if the ingot yield, plus the scrap recovered subtracted from 100 per cent. determines the loss, a drop in yield may increase the loss or the scrap, and both contribute to a monetary loss. To be sure, one can subdivide these unaccounted for losses into various components, such as metallics in slag, free Fe in slag, spillage, etc., and thereby reduce the amount of losses considered as "unaccounted for." If empirical methods could indicate with some degree of accuracy all losses, however slight, the undetermined losses become appreciably smaller and resultant calculations will check actual

Jan 1, 1929

By Freeman Bishop

Having obviously cleared the way for fast confirmation by the Senate Interior Committee, the Administration recently named Elburt F. Osborn, vice president of Penn State University, as director of the Bureau of Mines. Interior Committee Chairman Henry M. Jackson (D of Wash.) has moved hearings on the nomination right along, forecasting that they will end in a confirmation. Dr. Osborn not only made a good impression on the Committee, he also made it amply clear that he would be the boss of his job and have right-hand aides to help straighten out conflicts stemming from recently enacted health and safety regulations for miners. Mining engineers in the field hope this clarification can come soon. They are frankly fed up with local, state, regional and national overlapping of restrictions.

Jan 1, 1970

By M. R. Geer, J. D. Davis, H. F. Yancey

ALTHOUGH the mechanical cleaning of coal is carried out at plants on the surface, preparation is actually begun at the face in the mine. Here the character of the coal and the amount, character, and distribution of the impurities within the bed may be seen. Blasting methods, dust-allaying procedures, location of mining cut with respect to bands of impurity, and the practice of discarding segregated impurities underground, all have an important bearing on the successful operation of surface cleaning units. The most important single characteristic of both coal and its associated impurities from the standpoint of cleaning is specific gravity. Other characteristics related in one way or another to the preparation of coal are rank, petrographic composition, structure and hardness, and friability. These and still other coal properties are discussed in the first section of this chapter and impurity characteristics in the second. COAL CHARACTERISTICS RELATED TO PREPARATION Rank As a result of work done over a period of several years by committees of the American Society for Testing Materials and the American Standards Association, standard specifications are now available showing the classification of coals according to rank and quality of grade. The term "rank" expresses the degree to which the original coal-forming material has been changed by metamorphism through successive stages from peat to anthracite. Table 1 shows the classification of coals according to rank as devised by the committees of the organizations mentioned. The basic scheme of classification for the higher-rank coals is according to fixed carbon content, calculated to the dry, mineral-matter-free basis. Groups of lower rank are divided

Jan 1, 1950

By P. F. Gnirk, J. B. Cheatham

An experimental investigation has been made to study the effects of tooth angle and confining pressure on the force required for indentation of dry rock samples under confining pressure. In these experiments static single-tooth indentations were made on two standstones, a limestone, a schist and a slate under confining pressures of 5,000 to 15,000 psi. Sharp wedge-shaped teeth with included angles ranging from 30°to 105°were used. In all cases the force-displarenzent curves are approxinlately linear for rocks tested under confining pressure, as contrmted with the discontinuous curves obtained for silnilar rocks at atmospheric conditions. Photonzicrographs of thin sections through the craters indicate very little evidence of chip formation during indentation. In general the experimental data lie between calculated values for perfectly rough and perfectly smooth tooth-rock interfaces. INTRODUCTION The variables associated with ctrilling at depth are numerous and, in many instances, are not easity isolated and controlled. Also, many of these variables are interdependent; however, if the variables which are sufficiently independent of each other are held constant and are appropriately introduced, the dependent variables can be more easily studied and evaluated. It is the purpose of the present investigation to study experimentally the simplest case of bit tooth-rock interaction. In essence, the experiments have involved the static loading of sharp wedge-shaped tools on the surfaces of effectively semi-infinite dry rock samples subjected to confining pressures. During this investigation the following quantities have been maintained constant: 1. Pore pressure: atmospheric (i.e., the rock is dry). 2. permeability: although the rocks may be permeable, they are "jacketed" in such a manner that the fluid is not permitted to flow through them. 3. Temperature: 75F. 4. Rate of loading: essentially static (approximately 0.002 in./second). 5. Bit tooth: a sharp wedge-shaped tooth loaded normal to the rock surface. 6. Rock surface: smooth and flat. 7. Drilling fluid: hydraulic oil. In addition to the above conditions, the rock surface was free of a layer of cuttings. There was no indexing to previously indented surfaces, and the influence of corners of the borehole was neglected because the rock samples were effectively semi-infinite. The following quantities have been varied, and the resulting effects have been studied: 1. Rock a) Type (e.g., limestone, sandstone, etc.). b) Mechanical properties ) Necessarily dependent c) Porosity on type of rock. 2. Bit tooth (included angle of wedge-shaped tooth). 3. Depth of penetration. 4. cobfining pressure. On the basis of laboratory experiments which have shown that many rocks exhibit ductile behavior at confining pressures corresponding to depths usually reached during drilling,'.' a theory has previously been advanced which predicts the force required for penetration by a single sharp wedge tooth into a ductile* material.' The material is assumed to be isotropic, homogeneous and rigidly plastic (no elastic deformation) and to obey the Coubomb yield criterion (Figs. 1 and 2). Equations governing the force required for penelration are given for two extreme cases:** 1. A smooth, perfectly lubricated tooth-rock interface (fridionless boundary), in which the solution gives a minimum value for the penetrating force: in which F = force of the tooth, b = length of tooth edge,

By K. Kim

INTRODUCTION A thorough evaluation of the geologic material being considered must be conducted to determine the feasibility of constructing a large-scale underground facility in a deep geologic formation. The design and construction of a nuclear waste repository in basalt, due to the unprecedented nature of the project, adds significantly to the need for thoroughness of this evaluation and mandates that geoengineering data and analysis be of the highest quality. The investigations required to collect the data encompass in situ measurements and observations, as well as laboratory and field tests. Mathematical (numerical) models, which are required to predict the long-term performance of the repository structure, must be developed to evaluate rock mass behavior at canister, room, and repository scale and eventual 1 y must be validated through in situ tests and monitoring. The information generated from these geo- mechanics investigations is essential for assessing site suitability and will be utilized in the development of the repository design, the engineered barrier design, and the evaluation of repository performance. The Hanford Site near Richland, Washington is one of nine sites throughout the nation being investigated by the U .S. Department of Energy as a possible location for the first high-level nuclear waste repository in deep geologic formations. The process of site characterization is currently in progress. If the site is nominated by the U.S. Department of Energy, an extensive program will be undertaken, the culmination of which will be a decision on the suitability of the site for waste disposal. There are a mu1titude of elements to the proposed site characterization

Jan 1, 1984

By Susan B. Leiter

That oxygen in copper has been a source of trouble is well known and that that trouble has been real in the commercial world has been shown by Fuller.' Moore and Beckinsale's paper2 at the annual meeting of the Institute of Metals in London, 1921, called forth considerable discussion. Prof. T. Turner expressed the opinion that it was not necessary to have cuprous oxide present in sufficiently large quantities to form either globules or seams in order to produce a bad effect if the copper were gassed. This brought up the question of the solubility of oxygen in copper and the authors desired to know whether there were any evidence of such solubility, because their experience was that whenever there was any oxygen in copper it was present in the form of free cuprous oxide, which was practically always in the form of globules. Later Hanson, Marryat, and Ford3 stated that 'for all practical purposes cuprous oxide may be regarded as insoluble in copper. However, they found particles of the eutectic to coalesce to form much larger particles. They suggested that cuprous oxide was actually slightly soluble in copper, for it was difficult otherwise to understand the mechanism by which such coalescence could take place. W. E. Ruder, in discussing that paper, said that his experiments had led him to conclude that a slight solubility must exist to allow for the ready coalescence of oxide particles, but conductivity tests convinced him that that solubility was very small. Nevertheless, there appeared to be a state of admixture of oxide with copper that closely resembled a colloidal mixture which at first was mistaken for a true solution and which usually existed at the grain boundaries. The purpose of this paper is to give the results of some investigations, begun in September, 1921, which would seem to show that although cuprous oxide may be only slightly soluble: (1) this solubility is sufficient

Jan 1, 1926

By William R. Webster

At the Richmond mecting in February, 1901, I presented for discussion the proposed rail-specifications of Committee No. 1 of the American Section of the International Association for Testing Materials, with a review of their work, and other matters relating to the heat-treatment and chemical composition of steel (Trans., xxxi., 455). In order to bring out the views of our members on the important points referred to, I offered for discussion the following questions and comments (trans., xxxi., 972): " 1. The advantages to be gained by using more metal in the flanges and web of the heavier sections of rails.

Jan 1, 1903

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8'10'11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969