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By S. F. Reiter, W. R. Hibbard

A survey of the effect of heat treatment on the room temperature hardness of Fe-Mo alloys has been made. Constant strain rate tensile tests were performed between room temperature and 1800°F. These data were analyzed to determine the effect of temperature and composition on the strain hardening coefficient and strain rate sensitivity. Constant load creep-rupture tests were made on these alloys and the results related to composition and structure. A relation between the high temperature strength of the precipitation hardened alloys and the volume of precipitate has been observed. IN view of the extensive use of ferritic materials at elevated temperatures, it is surprising to note the limited amount of information relating the variables of plastic deformation, i.e., composition, structure, temperature, stress, strain, and strain rate. Hollomon and Lubahn' showed how the several variables of plastic flow might be treated analytically. No data were available on carbon-free iron and its alloys in a form suitable for this analysis. Several German investigations2-" constitute most of the experimental work relating high temperature properties to the constitution of these types of materials. In order to obtain new data, the iron-rich alloys of the Fe-Mo system were selected for detailed investigation for the following reasons: 1—Some of the important effects of molybdenum on the mechanical properties of iron have already been studied.' , 821 2—By suitable heat treatment of selected alloys, it is possible to study strengthening effects of four types: AT -a transformation, B—substitutional, C—precipitation, and D—dispersion of hard inter-metallic compound. Materials and Treatment Four-pound ingots were vacuum cast, employing the same melting schedule previously used.? The raw materials were electrolytic iron and lamp-grade molybdenum. The ingots were forged to l/z in. sq. rod and one portion swaged to 0.350 in. diam rod for the production of 1 15/16 in. long button-head specimens. The button-head specimen blanks were solution treated for 16 hr at 2100°F in hydrogen of —70°C dewpoint and then water quenched. They were subsequently plunge ground to the standard 0.160 in. diam test bar. Micrographs of the solution treated alloys are given in Figs. la through Id. The higher molybdenum alloys contained large equiaxed ferrite crystals similar to those in Fig. Id. A portion of the % in. rod was hot rolled to 0.100 in., sandblasted, and cold rolled to 0.020 in. Strip tensile specimens having a 0.020x0.200 in. cross-section and a 2.25 in. gage length were machined from the sheet. The alloys containing molybdenum were subsequently annealed 1 hr at 1560°F. The iron strip was annealed 4 hr at 1300°F in wet hydrogen. The resultant structures are shown in Fig. 2a through h. The ASTM grain sizes were 1 to 3 as solution heat treated or 3 to 4 as annealed. The chemical analyses of the alloys are given in Table I. Carbon contents were obtained after the heat treatments in hydrogen. Alloy 15.9 pct Mo was tested as a cast alloy.'

Jan 1, 1956

By Lauren A. Wright

SINCE the early nineteen-thirties the production of talc* in California has increased five-fold to a yield in 1947 of about 76,000 tons (fig. 1); conse- .' Unless otherwise qualified, the term "talc" in this paper will imply a mixture of the pure talc with such related minerals as commonly occur in the commercial material. quently the state is now one of the nation's three principal talc producers. The 1947 output, which represented about one-sixth of the national total for that year, was approximately equal to production from Vermont, and was second in value to that from New York. New York has an annual output of about 130,000 tons. Three factors have been mainly responsible for the expansion of talc production in California. (1) Technical advances and innovations, particularly in the ceramic industry, have increased the demand for certain California talcs. The nation's high-qual- LAUREN A. WRIGHT, Junior Member AIME, is Associate Geologist, California Division of Mines, San Francisco, Calif. Los Angeles Meeting, October 1948. San Francisco Meeting, February 1949. TP 2622 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscripts received Dec. 7, 1948; revision received Aug. 29, 1949. This paper is Contribution No. 508 of the Division of Geological Sciences, California Institute of Technology, Pasadena, Calif. the industry, mainly through demand for the urgently needed steatite. Fibrous talc, used as a paint extender by the armed forces, also was produced in quantity. (3) Expanding western industry has continued to draw heavily on California talc deposits, and has extended the upward production trend into the postwar period. Considerably more than half of California's current talc output is used as ceramic raw material. The paint, rubber, paper, and textile industries are the more important consumers of the remainder. Smaller amounts are used as insecticide carriers, and in cosmetics, and various minor industrial applications. During World War I1 the principal steatite deposits were studied in detail by members of the U. S. Geological Survey; other sources of commercial talc in the state have in the past received but scant geologic attention. The following discussion is essentially a preliminary report based on research currently in progress by the California Division of Mines, and includes a brief outline of previous steatite studies by the U. S. Geological Survey. Distribution of California Talc Deposits: The principal talc resources of both California and Nevada are confined to an elongate belt that extends from the vicinity of Baker, in north-central San Bernardino County, northwestward to include the southern Death Valley region, the Inyo Range, and the Palmetto-Oasis district of western Nevada (fig. 2). This belt, of which all but the northernmost tip lies in California, is approximately 200 miles long and 30 miles in average width. Included in the belt are four contrasting areas. The deposits within each area are geologically similar and yield talcs that have characteristic properties and applications. Three of these local "talc provinces" lie within California's portion of the talc-

Jan 1, 1951

By Lauren A. Wright

SINCE the early nineteen-thirties the production of talc* in California has increased five-fold to a yield in 1947 of about 76,000 tons (fig. 1); conse- .' Unless otherwise qualified, the term "talc" in this paper will imply a mixture of the pure talc with such related minerals as commonly occur in the commercial material. quently the state is now one of the nation's three principal talc producers. The 1947 output, which represented about one-sixth of the national total for that year, was approximately equal to production from Vermont, and was second in value to that from New York. New York has an annual output of about 130,000 tons. Three factors have been mainly responsible for the expansion of talc production in California. (1) Technical advances and innovations, particularly in the ceramic industry, have increased the demand for certain California talcs. The nation's high-qual- LAUREN A. WRIGHT, Junior Member AIME, is Associate Geologist, California Division of Mines, San Francisco, Calif. Los Angeles Meeting, October 1948. San Francisco Meeting, February 1949. TP 2622 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscripts received Dec. 7, 1948; revision received Aug. 29, 1949. This paper is Contribution No. 508 of the Division of Geological Sciences, California Institute of Technology, Pasadena, Calif. the industry, mainly through demand for the urgently needed steatite. Fibrous talc, used as a paint extender by the armed forces, also was produced in quantity. (3) Expanding western industry has continued to draw heavily on California talc deposits, and has extended the upward production trend into the postwar period. Considerably more than half of California's current talc output is used as ceramic raw material. The paint, rubber, paper, and textile industries are the more important consumers of the remainder. Smaller amounts are used as insecticide carriers, and in cosmetics, and various minor industrial applications. During World War I1 the principal steatite deposits were studied in detail by members of the U. S. Geological Survey; other sources of commercial talc in the state have in the past received but scant geologic attention. The following discussion is essentially a preliminary report based on research currently in progress by the California Division of Mines, and includes a brief outline of previous steatite studies by the U. S. Geological Survey. Distribution of California Talc Deposits: The principal talc resources of both California and Nevada are confined to an elongate belt that extends from the vicinity of Baker, in north-central San Bernardino County, northwestward to include the southern Death Valley region, the Inyo Range, and the Palmetto-Oasis district of western Nevada (fig. 2). This belt, of which all but the northernmost tip lies in California, is approximately 200 miles long and 30 miles in average width. Included in the belt are four contrasting areas. The deposits within each area are geologically similar and yield talcs that have characteristic properties and applications. Three of these local "talc provinces" lie within California's portion of the talc-

Jan 1, 1951

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the re crystallization temperature of nickel has been investigated. All additions raised the re crystallization temperature. Both the rate of change of re crystallization temperature with at. pet solute and the limit of initial linearity are found to correlate with the free atom ground state outer electron configuration of the solute element. A comparison of all of the correlations for the transition elements studied has yielded a set of empirical relations, which allows the prediction of the effect of dilute binary transition elements on the recrystallization temperature of other transition elements. The work of Abrahamson, et al.1-7 on dilute binary solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and re-crystallization temperature. Further, it has been shown3,4 that the limit of initial linearity may also be correlated with the solute electron configuration. Since previous studies have dealt with bee and hexagonal base elements, this study is made to note what effect, if any, the fee base structure might have. Nickel also serves to give a solvent configuration which will allow the comparison of all of the transition element solvents. Olsen8 has studied the effect of some trace elements upon the recrystallization of nickel. He included only Ti, Zr, W, Mn, and Co of the transition elements. The differences in change of recrystallization temperature were attributed to the solute atom size and to the solubility of the solute in nickel. PROCEDURE All alloys were made using 99.9 + pet Ni with 0.003 C, 0.015 Fe, 0.007 0, and 0.0007 H. The solute elements were 99.9 + pet pure. According to the published binary phase diagrams9 and metallo-graphic examinations at X750, all solute elements were in solid solution. The alloys were arc melted and remelted four times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot forged at 800oC to 0.750 in. diam, machined to 0.60 in., vacuum annealed for 1 hr at 700°c, swaged to 0.40 in. and annealed at 700oC for 1 hr in vacuum. The grain size was checked and found to be 77 * 20 grains per sq mm. The specimens were then swaged to 0.187 in., yielding 76 ± 1 pet cold work. All alloys were then chemically analyzed for the solute addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The swaged rod was cut into 8.25 in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was maintained at 250" to 850°C over an eight inch length, recorded by twelve thermocouples. Control was ± 3oC, accomplished at the hot end. The recrystallization was determined metallo-graphically over the entire specimen. The criterion chosen was that point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be generally ± 3oC.

Jan 1, 1962

By N. F. Schulz

The purpose of this investigation was to evaluate the effects of variables in equipment and procedure on tube test results. This information was then to be used to formulate specifications, preferably within the practical ranges of existing machines, for test procedures capable of yielding precise and meaningful data concerning the magnetic separation of any magnetite ore, regardless of its origin. A survey of current practice was conducted among laboratories using the Davis tube test. Many tube tests were performed to experimentally evaluate the variables most likely to affect test results. A simple method was then sought for adequately interpreting tube test results. The Davis magnetic tube concentrator is a laboratory machine designed to separate a small sample of pulverized magnetic iron ore into magnetic and non-magnetic fractions. It was developed in 1921 by mechanization of a test previously performed manually No significant changes have been made in the design of the apparatus since that time. The Davis magnetic tube test continues to serve as a practical basis for judging the amenability of an ore to magnetic separation and for controlling magnetic separation plant operations. The apparatus consists of an inclined cylindrical glass tube supported adjacent to closely spaced pointed poles of a powerful C-magnet. (Fig. 1). To conduct a tube test, a sample of suitably prepared ore is poured into the water-filled tube. With wash water flowing through, the tube is oscillated to gradually reject the non-magnetic and weakly magnetic ore particles until the desired degree of separation is attained. Both the magnetic concentrate and the tailings may be recovered for examination. MAGNETIC SEPARATION BY THE DAVIS TUBE Mechanical separation of a specified mineral component from an ore usually requires comminution to fine sizes for sufficient liberation. Some distinguish- ing property of the mineral is then exploited to sort the desired mineral particles from the gangue particles. The magnetic separation of iron ores is based on the fact that magnetite, Fe3O4, is strongly attracted by a magnetic field while the gangue minerals are not. Maghemite, ?-Fe2O3, which may occur in certain chemically processed ores, responds similarly to magnetite. The magnetic process is practical only when the loss of iron in the form of relatively nonmagnetic hematite, Fe2O3, goethite, Fe2O3.nH2O, or other iron mineral can be tolerated. In the Davis magnetic tube concentrator, magnetic attraction holds magnetically susceptible particles in a magnetic field. Forces due to gravity, inertia, and fluid-solid friction tend to remove the less susceptible particles from the field. The probability that a given middling particle will be rejected from the tube in a given period of time is an inverse function of its magnetite content, with some modification due to particle size and mineral specific gravities. The net result is that ore particles tend to be rejected in their order of increasing magnetite content, while the retained portion or magnetic concentrate increases in grade continuously during the process. MAGNETIC SEPARATION CHARACTERISTIC The magnetic separation characteristic or MSC of a magnetite ore is the correlation between concentrate

Jan 1, 1964

By E. W. Hart, W. R. Hibbard

The room temperature flow characteristics of a series of Cu-Cr alloys are found to be related to the amount and characteristics of the chromium-rich precipitate. The results are consistent with the theory of Fisher, Hart, and Pry, which considers the trapping to dislocation loops around precipitate particles. THE use of dispersed phases for hardening metals, particularly high temperature alloys, has been practiced for several years. Current theories describing the effects of dispersions on the basis of dislocation theory have been proposed by Mott and Nabarro.l-4 rowan," and Fisher, Hart, and Pry.8 These theories recently have been discussed by Hart,' who pointed out that the experimental data available for comparison with theoretical calculations for overaged alloys are confined to studies by Gensamer, Pearsall, Pellini, and Low,8 Shaw, Sher-by, Starr, and Dorn,9 and some hitherto unpublished data on Cu-Cr alloys which will be described herein. Certain difficulties were associated with the interpretation of the first two studies. Gensamer, Pearsall, Pellini, and Low were concerned principally with interparticle spacing and did not document particle sizes. Shaw, Sherby, Starr, and Dorn included all the data in their report which was necessary for the theoretical evaluation, but their study is subject to some question1" due to difference in prior history of various specimens and due to systematic differences in particle characteristics" which appeared to be associated with differences in the magnification of their microscopic examination. The current study was undertaken to obtain critical data in a manner which avoids some of these limitations. Specimens of eight Cu-Cr alloys remaining from a previous investigation'' were available in the form of 100 mil sheet of the compositions shown in Table I. At 200 mil this material had been previously an- nealed ½ hr at 1000°C, water quenched, and cold rolled 50 pct. Samples were further cold rolled to a thickness of 20 mil for a total reduction of 90 pct. Sheet tensile specimens of standard geometry with a gage length 2½ in. long and 0.20 in. wide were machined from this sheet. These specimens were then annealed in a dried N2-H2 atmosphere for the times and temperatures indicated in Table I. This anneal served two purposes: 1—to obtain a fairly uniform and nearly constant grain size of 0.015 to 0.022 mm average diameter, and 2—to precipitate a fairly uniform, nearly spherical over-aged dispersion of essentially pure chromium. A typical microstructure illustrating the grain size and the uniformity of the dispersion is shown in Fig. 1. A typical dispersion illustrating the range of sizes and shapes of the particles is shown in Fig. 2. The tensile specimens were tested in the Instron equipment described in ref. 11 at room temperature at a strain rate of 0.04 in. per in. per min. Three tests were run on each alloy with sufficient repro-ducibility that a single true stress-true plastic strain curve could be drawn through the three sets of data for each alloy. Typical curves are shown in Fig. 3.

Jan 1, 1956

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By E. E. Donath

THE coal hydrogenation process is well known as a means for the production of liquid fuels -from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aromatics and of tar acids and tar bases. The relative amounts of heavy and middle oil-boiling above and below, e.g., 325°C-can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.1 Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydro¬gen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catch-pot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1952

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By T. D. Teimann, R. L. Stone

The rate of extraction of silica from certain Wisconsin and Minnesota taconites was investigated by autoclave digestion in sodium hydroxide solutions over the temperature range from 296° to 416°F. Rates obtained were from 7 to 254 g mol per cm2 per sec giving activation energies from 15,000 to 19.000 cal per mol. Activation energy was found to increase with increase of sodium hydroxide concentration. Digestion of different forms of quartz indicated the rate of extraction to be solely a function of surface area under similar conditions of digestion. The results of an experimental investigation on the caustic extraction of silica from certain Wisconsin and Minnesota taconites were presented in a recent publication.' It was shown that residual concentrates containing as much as 65% iron can be produced by this method. The occurrence of silica as a micro-crystalline variety of quartz with high specific surface area gave correspondingly high mean rates of extraction in solutions of sodium hydroxide. The present paper extends this previous work by presenting the results of a study of the specific rates of extraction of silica from these ores as related to temperature, sodium hydroxide concentration and variety of quartz. Calculated activation energies for the dissolution of silica are presented and some possible mechanisms are discussed. TACONITES The low-grade siliceous iron ores investigated included taconite from the Wisconsin Gogebic range and a semi-taconite2 from the Minnesota Mesabi range. These are adequately described in the former paper1 and by the U. S. Bureau of Mines. The principal iron minerals are hematite (Fe2O3) and goethite (Fe2O3 . H2O), while the gangue is essentially a microcrystalline variety of quartz. Minor amounts of other minerals are present. Typical analyses show the Wisconsin taconite to contain approximately 28% Fe and 54% SiO2 and the Minnesota semi-taconite 39% Fe and 39% SiO2. Analyses of the actual samples used are given in Table I. The taconite samples were prepared for digestion by reducing the original ore to minus 200 mesh in a Braun pulverizer. QUARTZ Three varieties of quartz were studied in the investigation: Ottawa sand, chert and chalcedony. The Ottawa sand was obtained from the Ottawa Silica Co. The chert and chalcedony came from Wards Natural Science Establishment. A minus 200 plus 400 mesh fraction of the Ottawa sand, used as a surface area standard, was repeatedly washed in hot concentrated hydrochloric acid followed by distilled water before autoclaving. The other two varieties were used directly after grinding through 200 mesh in a laboratory hammer mill. Analyses of these samples appear in Table 11. Microscopic examination of the silica samples by the oil immersion method showed that the Ottawa sand consisted of clean, uniform spheres of quartz with little deviation in size from a mean diameter of 82µ determined by a distribution count. The other two varieties consisted almost entirely of microcrystalline aggregates of quartz crystals; the aggregates ranged from 10 to 70µ. The individual crystals in the chert aggregates were estimated to be of the order of

Jan 1, 1964

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By Morris Muskat

It is pointed out that the application of capillary pressure curves obtained by drainage or desaturation processes to the calculation of the fluid distribution in interphase transition zones involves a number of difficulties; namely: (I) the development of very low nonwetting phase saturations appears to be in contradiction with the lack of mobility of such distributions indicated by permeability-saturation curves, (2) dispersed nonwetting phases are thermodynamically unstable, and (3) discontinuous phases should not be subject to hydrostatic equilibrium requirements. While these difficulties could be obviated by assuming that the capillary pressure drainage curve has an initial horizontal segment, they are automatically circumvented by application of the imbibition capillary pressure curve to the lower part of the water-oil transition zone. These generally show zero displacement pressure at only partial wetting-phase saturations. The countercurrent upward flow of oil into the main oil-saturated pay and downward drainage of water also suggests that wetting phase imbibition processes will control the saturation distribution immediately above the water-saturated section. Similar considerations, with a generalized interpretation of the apparent wetting-phase behavior of the oil and gas phases, provides a basis for constructing the curve for fluid distribution in the oil-gas transition zone. In the transition zones so derived, the oil begins with a nonvanishing saturation at the water-oil contact and terminates with a similar saturation at the top of the gas-oil contact. The gas-oil transition zone begins with an equivalent nonvanishing gas saturation. Introduction It has been a common assumption for some years that the nature of the fluid dis- tribution in virgin reservoirs, and in particular that in the transition zones between the oil and water and between the oil and gas sections, can be computed by a simple application of capillary pressure data. The results of such calculations appear to have been first reported by Leverett.' The latter, however, indicated only the numerical values of the parameters used in the computations, without explicitly describing the procedure. Leverett's illustrative calculated transition zones are reproduced in Fig I. Although no critical study of the apparently obvious method of calculation has been published, one cannot proceed very far in the computation without encountering some rather fundamental questions not yet answered in the literature. This paper is not written under the pretense that the whole transition-zone problem has been fully and satisfactorily solved. Its purpose, rather, is to discuss suggestions for its treatment, much of it admittedly hypothetical, and emphasize the nature of the uncertainties arising therein; for the literature, as now available, gives little indication that there are any problems still outstanding. The Transition-zone Equation The basic equation, which presumably gives directly the fluid distribution without recourse to any further consideration, is: Ap = (r1 - r2)gh [1] where r1, y2 are the densities of the two contiguous fluids, h is the height above the "capillary-free" zone of complete saturation with fluid I, g the acceleration of gravity, and Ap is the capillary pressure across the average interface at the height

Jan 1, 1949

By C. F. Knutson, Martin Felsenthal, J. D. Lung, J. D. Sudbury

This paper has been written to summarize the laboratory and field studies leading to injection of Pacific Ocean water into the Third Grubb formation. Laboratory tests for studying the permeabilities of cores to Pacific Ocean water are described. Resu1ts of these tests showed that the water could be successfully injected if it is chertzically stable, sterile, and properly filtered. Clay swelling was shown to be a comparatively minor factor in permeability reduction. Studies leading to development of an economical system for properly conditioning the ocean water are discussed. It was necessary to control pH, calcium carbonate deposition, bacterial growth, iron solubility. oxygen, and suspended .solids. A relatively simple system combining the use of sulifur dioxide, a quaternary rlmmonium chloride, and filtration was shown to adeqrrately control all these factors. This combination has not previozrsly been used as a water treating technique. Evaluation tests of the water conditioning system prior to injection are described, and results of such tests are presented. Control measures needed to insure a continusously adequate water treatment are reviewed. INTRODUCTION The utilization of sea water for waterflooding has only recently been attempted. Knowledge of treating requirements has been limited, and in most cases no water treating has been done. Prior to the initiation of the Third Grubb zone pilot water flood at Ventura, Calif.,1,2 extensive laboratory research was done in an effort to define the treatment necessary to provide a suitable injection fluid. Close coordination and cooperation between field and research personnel were found to be the foremost requisites in developing the most economical and practical method for treating ocean water. LABORATORY STUDIES Plugging Tendencies of Untreated Ocean Water A program of laboratory studies was initiated for the purpose of evaluating whether ocean water could be injected into the formation for prolonged periods of time without causing plugging of the pore spaces of the formation. Because of the fairly low permeability of the formation (averaging about 40 md), it was realized from the outset that a water of exceptionally high quality was needed. Ocean water used in the laboratory studies was carefully filtered through ultrafine fritted glass filters, having nominal maximum pore sizes of 1.4 microns. Permeability tests were then performed on representative core material from the formation. It soon became apparent in these tests that filtration alone was not a sufficient treatment for the ocean water. Prolonged injection of the filtered water caused rapid plugging of the core samples. The permeability decline of a typical sample is illustrated by Curve A in Fig. 1. The several factors which can contribute to this plugging tendency are briefly reviewed below: Interaction with Formation Clays An evaluation of clay swelling effects on liquid permeability was made using core samples from the Grubb formation. An oil was chosen for determining the reference liquid permeability because it would not tend to react with any clays that might be present in the formation. The samples were then extracted, dried, and resat-urated with either treated ocean water, formation water, or fresh water. Permeabilities to the various waters were then determined. Results of this test series are summarized in Fig. 7. The difference between the oil permeability and water

Jan 1, 1957

By H. Papazian, Robert A. Lad

SINCE it can be shown both theoretically'' : and experimentally that disordered Cu3Au has a greater internal energy than the ordered alloy, it might be expected that its chemical reactivity would be greater. Experiments were initiated' to test this hypothesis. This note will describe some recent results obtained in the study of the rates of corrosion of ordered and disordered polycrystalline Cu3Au by aqueous FeCl., The work of Robertson' has indicated that the attack by such solutions is intergran-ular and highly orientation dependent. It was of interest to see whether the order-disorder effect was great enough to overcome the variations from specimen to specimen which would arise from this type of attack. The polycrystalline alloy specimens (0.020 in. wire, 1¾ in. long) were preannealed in ½ atm H, at 700°C for 2 hr. The subsequent heat treatments to produce order and disorder were performed in M atm He. Disordered specimens were obtained by heating at 450°C for 2 hr and quenching in water. Ordered specimens were produced by heating for 2 hr at 450°, furnace cooling to 380°, and soaking at 380°C for 80 to 90 hr. Room temperature was reached by cooling to 150" at a rate never exceeding 7" per hr, and water quenching from 150°C. The specimens so produced exhibited electrical resistivities characteristic of the two states; of the order of 11.27x10 ohm-cm for the disordered, and 4.28x10 ohm-cm for the ordered specimens. The corrosion rates were studied at 30°C in ferric chloride solutions of several concentrations (?,¼, 1.5, and 1 molar). The specimens were attached to a stirrer during the tests. Tests were interrupted at intervals, and the specimen weight change was determined after washing and drying. Analysis of the solutions showed that the attack was limited to the copper. The higher corrosion rate for the disordered alloy, as illustrated in Fig. l, is typical of the results obtained. The effect of variation in ferric chloride concentrations is indicated in Table I for typical specimens. The variations in the ratio of reactivity for disordered and ordered specimens at the different concentrations are within experimental error, and the best value is estimated to be near 1.4. The experimental variation was due in part to the mode of attack, as mentioned, and in part to the fact that films were formed on the specimens under some conditions. Electron diffraction patterns of the films were very complex and indicated the presence of metallic iron, as did chemical analysis. In an attempt to eliminate the difficulties arising from the mechanism of attack, single crystal specimens were used. A greater reaction rate was again measured for the disordered specimens, but the reproduci-bility was no better than that for the polycrystalline metal. This would indicate that film formation was primarily responsible. It was concluded that the reaction with aqueous ferric chloride served to demonstrate that the reactivity of disordered Cu3Au is greater than that of the ordered alloy. However, the difficulties with film formation did not permit determinations of a precision great enough to warrant extension of the study to partially ordered alloy systems.

Jan 1, 1957

By E. A. Has, E. Mcl. Tittmann

Double roasting of sinter carrying a high percentage of lead concentrates, gave rise to the problem of removing the sheets of metallic lead formed in the wind boxes. The solution of the problem has been found in the water sealed wind boxes. The metallic lead is granulated and can be removed without seriously interfering with the operation of the machine and eliminates necessity of men going in wind boxes with air guns. THE practice of double sintering the charge for lead blast furnaces, which is now standard throughout the lead smelting industry, has introduced the rather difficult problem of cleaning the wind boxes on sintering machines used for the final pass. Two factors have more recently accentuated this problem: (1) the growing demand of workmen for better working conditions and less arduous labor, and (2) the growing dearth of crude lead ores and the improved grade of lead concentrates demand a charge carrying the maximum percentage of lead. One to 2 pct of such high lead charges (30 to 40) when processed on machines in reasonably good condition will pass through the grates and report in the wind boxes. One-half to three-quarters of this material will be metallic lead reduced by the coke breeze or other fuel mixed with the charge. This lead forms large cakes or chunks which are hard to remove and which substantially increase the time the machine is out of operation for cleaning the wind boxes. A high lead fall can reduce the operating time 30 pct. As a specific example, a 30 ft machine having 63 in. pallets, and equipped with three conventional wind boxes, requires 3 to 4 hr per day for removing the accumulation in the wind boxes when operated as a final pass machine. This same machine when operated on raw charge requires less than an hour per day for cleaning. To eliminate formation of large chunks of lead in the wind boxes of the final pass machines and time lost in cleaning the boxes, R. C. Rutherford of the Chihuahua smelter of the American Smelting and Refining Co., devised and patented* a wind box having a water bath to granulate the lead as it falls from the grate bars. Later, C. H. Harris of the San Luis plant made and patentedt an improvement on Rutherford's device in which the water bath seals the wind box in a manner permitting the latter to be readily cleaned without destroying the vacuum. The first machine to our knowledge to use the water bath box was at the Chihuahua plant along the lines of the Rutherford patent. In 1942, a machine was placed in operation at the El Paso plant which incorporated the features of both Rutherford and Harris. This machine is 40 ft long equipped with pallets 63 x 24 in., and having 4 wind boxes 10 ft 4 in. x 7 ft 2 in. x 51 ft 3 in. in size (fig. 1). The air from the fourth box is returned to the first three, and the gas from the first three discharged to a baghouse. The machine has conventional drive, discharge hopper,

Jan 1, 1951

By N. E. Grosvenor

Several methods have been proposed for determining the tensile strength of rock. These have been tried out over the past several years, but the results have been erratic and of doubtful value. The tensile strength of rock is its weakest property, and this property apparently enters into all failure phenomena, whether underground or on the slope of an open pit. Therefore, it is essential that detailed quantitative information is known about the tensile strength of rock if the design engineer is going to select the proper pit slope, pit orientation, or orientation of underground workings so as to give the most economical and safest mining condition. This quantitative information may be used to orient the pit in such a manner as to allow steep slopes along two sides. This information possibly may be used to orient the direction of either underground workings or open pits so as to decrease powder consumption and to increase blasting efficiency. Hence it is of prime importance that a method of determining accurately the tensile strength of rocks be developed. The U. S. Bureau of Mines states' that no standard methods have been proposed by the ASTM for testing the tensile strength of rock. The method described in the Bureau publication is said by them to be unsatisfactory. A similar test that has been used in our laboratory in place of the USBM test is shown in Figs. 1 and 2. h this test the core is placed in a set of grips that has been designed for one particular size core. The grips are designed to distribute the stress around the core if they are tightened correctly. A universal joint or a flexible cable may be used in conjunction with the apparatus to prevent bending or twisting of the specimen. The main difficulty encountered with the system shown is the failure of the specimen within the grips. The possible cause of the failure within the grips may be due to a stress concentration set up by the uneven tightening of the grips. This method can be used only for tests on cores, and even then has been found to be totally unsatisfactory because of the failure within the grips. The U. S. Bureau of Reclamation has been using a test similar to the sketch shown in Fig. 3. Sulfur is cast around each end of the specimen to form a bearing surface and then a ring grip is used to apply a tensile stress. The grips are in contact with the sulfur cast and do not touch the specimen. This method is unsatisfactory, apparently because a large number of the specimens appear to break within the sulfur cast. Professor Wuerker of the University of Illinois uses the test shown in Fig. 4.' Professor Wuerker states2 that this method has given definite and reproducible results with the weakest as well as with the strongest rocks. The test is a supplement in all cases where cores cannot be obtained. The principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar. Soft

Jan 1, 1961

By G. D. Hobson, I. Mrosovsky

Material balance relationships for expansion-type reservoirs above the bubble point have been discussed in recent years by H. N. Hall and M. F. Hawkins, Jr. The former drew attention to the effects of rock compressibility, and the latter to the effects of the compressibility of any interstitial water. Hawkins derived a general relationship which took note of oil, water and rock compressibilities, and then by assuming first, the absence of interstitial water and secondly, no effects due to interstitial water or rock compressibility, obtained relationships symbolically of the same form as those previously derived directly by Hall. Hawkins defined his terms clearly, and noted an approximation, due to the omission of a term involving the product of two compressibilities, made in reaching his final equation. There is, however, possible ambiguity with regard to Hall's written definition of the oil production term. One interpretation would mean that the produced oil and initial oil-in-place, if both required as stock tank barrels, would be obtained by using different formation volume factors in the conversion in order to satisfy the conditions implicit in Hall's formulae. The other would involve an approximation which, if used, was not stated. In both Hall's and Hawkins' studies the effect of the approximation or inconsistency is very slight. Nevertheless, it may be justifiable to give a somewhat more consistent derivation, since the complexity of the final relationships is not thereby greatly increased. Let the initial pore volume be Vi and the volume after a pressure drop of Ap, V. Then V = V, (1 - ?p . cr), where c, is the rock compressibility expressed as change in pore volume/unit pore volume/unit pressure change, and is defined with the initial pressure as base. Suppose that the interstitial water saturation under the initial conditions is Sw. The total volume of interstitial water under those conditions will be ViSw. If the volume of the water after dropping the pressure by ?p is V., this will be given by Vw = ViSw (1 + ?p.c,w), the compressibility of the water being c, which is ex- pressed using the volume at the initial pressure as base. If Boi is the reservoir volume factor of the crude oil for the initial reservoir conditions, and B. the equivalent factor when the pressure has dropped by ?p, with N the initial amount of oil expressed as stock tank barrels. N.Boi = Vi - V,Sw If n is the amount of oil produced (in terms of stock tank barrels) as a result of the pressure drop ?p, the remaining subsurface volume of oil at the lower pressure will be Bw, and Bc can be related to the compressibi:ity of oil and the pressure drop, and if c, is the compressibility factor based on the initial conditions, The relationship derived by Hawkins was case to a standard at the lower pressure, while a term (Ap) had been dropped, because of its smallness arising from its dependence on the products of two compressibility factors. When there is no interstitial water and rock compressibility can be ignored, Eq. 1 reduces to:

Jan 1, 1957

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By F. H. Wilson, R. M. Brick

WITH the papers of Palmer and Smith1 and of Burghoff and Bohlen,2 published in 1942, understanding of the problem of the development of ears on deep-drawn brass cups was brought to the point where, from a practical standpoint, producers of brass sheet could keep earing under control. However, these very practical results raised questions concerning the reasons for the observed behavior. Since plastic deformation is fundamentally a function of crystallographic slip, these reasons must be considered in the light of the textures to be found in the annealed sheet. Various attempts have been made to interpret the mechanism of ear formation by correlation with the preferred orientation and the anisotropy of the sheet. However, none of these has satisfactorily explained why ears are usually found in the rolling and transverse directions for copper but at 45° to these directions for brass. This paper offers additional data on these two related subjects and has been divided into two sections. The first section provides a survey of the recrystallization textures of brass as affected by annealing temperatures and prior reductions, and an account of the earing behavior which accompanies these textures. The second section reports new data on the anisotropy that accompanies a characteristic texture for brass and endeavors with partial success to establish the factors that account for the difference in earing behavior between copper and brass. EARING BEHAVIOR OF BRASS Review of Textures The recrystallization texture of severely rolled brass was first reported by Bass and Glocker.3 The preferred orientation to which this texture, obtained from metal annealed at 500°C., was most akin was (113)[112]. This texture has been confirmed by Bauer, von Göler and Sachs;4 Brick;* Brick, Martin and Angier;6 and Cook and Richards7 who, in general, used annealing temperatures under 500°C. Bass and Glocker3 also reported the recrystallization texture at 850°C. to be the same as at 500°C. They analyzed their textures by means of single photograms obtained with white radiation. The photograms for both temperatures are reproduced in their paper, and there is a strong similarity between the two. However, for the latter temperature, the number of spots registered on the film was remarkably large for the grain size to be expected, and the authors made no mention of using a technique that would integrate a large enough area of the specimen to produce so many spots. The only other attempt to determine textures resulting from high temperature

Jan 1, 1945

By A. Hultgren, B. Herrlander

The original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between A1 and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880' was free from veining. Bannister and Jones' considered veining in ferrite to be a manifestation of microscopical and sub-microscopica~ inclusions. NorthCOtt,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berg1und. TrittOn (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling. Slight distortion would not allow projecting parts of a growing crystal to join up with atomic symmetry. Hanemann and co-workers showed that veining in ferrite consisted of ridges

Jan 1, 1948