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By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By H. J. Rose, J. J. S. Sebastian

When coal is stored under ordinary conditions, progressive changes take place in its chemical and physical properties. These changes are largely caused by the reaction of atmospheric oxygen with the coal substance. Although this "oxidation" or "weathering" occurs slowly in the case of high-rank coals, it is nevertheless a matter of considerable importance, since even a small amount of oxidation may affect the value of coal for carbonization purposes. Coal storage is a necessity at all carbonizing plants. In normal times there are about 5,000,000 tons in storage at by-product coke ovens and gas retorts in the United States, as compared with an annual throughput of about 75,000,000 tons. In other words, the average coal reserve at such plants is slightly less than one month's supply. However, owing to the cost of storage and recovery, coal is usually left in stockpile for as long a time as the management thinks advisable. Storage for six to eight months is common practice and is, in fact, a necessity at certain plants which obtain their coal by water routes that are closed during winter months. Modern by-product coke ovens operate continuously, and they are not cooled down from the time that they arc put into operation until they are shut down for rebuilding—perhaps 20 years later. This continuous operation is imposed by silica-brick construction and high operating temperatures. It is therefore obvious that coke plants must at all times maintain an adequate supply of stored coal, in order to prevent a failure in supply from any cause whatever. Thus when strikes or other emergencies threaten, abnormally large coal stocks are accumulated and held at coke and gas plants. Many of these plants have been forced, at some time or other, to use coal that has been stored for several years. Such coal may fail to coke at all, or it may produce a dirty appearing, weak coke of reduced value. The yields of salable by-products may also be distinctly lowered. However, it must not be assumed that slight oxidation or heat effects are always injurious. Certain high-volatile coals produce a stronger, blockier

Jan 1, 1930

By A. E. Worthington, R. F. Meldau

An analog computer study was made of the reduction of the magnitude of the SP by formation geometry and resistivity effects. Practical field .situations were studied. The analog data were converted to the form of departure charts. These charts may he used to determine the reduction in the SP due to the above eflects pith good precision Quantitative interpretation of the SP log in terms of formation water resistivity is presently based on the premise that the observed SP is equal to the electrochemical potential developed across a shale between the mud filtrate and the formation water. This procedure inherently assumes that, first, no electro kinetic (streaming) potential is present, and, second, that the SP is not reduced by resistivity or geometry effects in the formation. When, however, such a reduction of the observed SP does occur, one may write, SP = b,E, b, E, (1) where SP is the observed self-potential opposite the center of the bed under consideration. In this case, E, is the electrochemical potential, E, is the electrokinetic potential, b, is the electrochemical reduction factor, and h, is the electrokinetic reduction factor. The first assumption above is equivalent to assuming E, = O in Eq. 1 and the second assumption is equivalent to h, = b, = 1. Examination of electric logs shows that for many formations of interest the observed SP is reduced below its maximum value. The object of this work is to aid quantitative SP interpretation in at least some of these situations by obtaining values for b, and b, in Eq. 1 as functions of realistic combinations of bed thickness, depth of invasion, and formation resistivity. The only previously published work in this field known to the authors is by H. G. Doll' in 1948. He evaluated b, under conditions permitting exact analytical solution. His work clearly established the importance and qualitative nature of formation geometry and resistivity effects upon the SP, but the necessity of obtaining analytical solutions restricted his study to situations of limited practical interest. In order to extend such studies to practical combinations of formation parameters which do not lend themselves to feasible analytical solutions, the results reported in this paper were obtained by use of a special analog computer. THE ANALOG MODEL The analog model used for this study was the Guyed Analog Computer which originally was designed and built for resistivity log departure curve studies. It consists of a two-dimensional mesh of resistors, with the vertical mesh corresponding linearly to vertical distance along the borehole, and the horizontal mesh corresponding to radial distance from the borehole axis. By proper choice of horizontal resistor values, a three-dimensional, axially symmetric, borehole-formation problem can be modeled with this two-dimensional array. These and other details of the model are contained in a paper by H. Guyod'. The geometry used for the SP studies with the analog is depicted in Fig. 1. This configuration has a horizontal plane of symmetry, and, hence, the model, and the following discussion, need only to be concerned with one quadrant such as shown in Fig. 2. A further simplification arises by considering that both the natural potential sources and those used in the model have fixed internal impedance. Therefore, the current flows produced by these sources can be separated and studied independently ( i.e., the superposition theorem can be applied). SP = SP, i SP, = h,E, + b,E, ,(7)

By Alexander L. Field

IN a previous paper,' the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of " red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the rettetion between zirconium and sulfur in molten steel may be represented by the simple equation, Zr + 25 = ZrS², and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion. Hot-rolling Properties of High-sulfur Steels with and without Zirconium The chemical composition of twenty-eight steel ingots embracing eleven heats made in a basic-lined electric furnace is shown in Table 1. The practice followed in the manufacture of these high-sulfur steels was described in the previous paper. Table 1 also gives the behavior of the

Jan 1, 1924

By C. J. Haigh

Stockpiled and currently produced zinc plant residues containing zinc ferrite are to be treated at a rate of 350 tonne per day in a plant that is being constructed at the Risdon works of the Electrolytic Zinc Company of Australasia Limited (E.Z.). Start-up of the plant is scheduled for December, 1970. The residue is to be treated by a hydrometallurgical process that was developed by E.Z. in Australia, by Det Norske Zinkkompani in Norway, and by Compagnie Royale Asturienne des Mines (Asturiana de Zinc) in Spain. The process, as it is to be used at Risdon, is simple, consisting essentially of two stages : 1. A leaching stage at atmospheric pressure in which the zinc ferrite contained in zinc plant residue is dissolved in spent electrolyte, fortified with make up sulphuric acid, at a temperature in the range 70 to 95ºC. Undissolved solids containing lead and precious metals are separated for sale to a lead smelter. 2. An iron precipitation stage at atmospheric pressure in which ferric iron is precipitated from a slightly acidic solution at 90 to 95ºC as ammonium jarosite, a crystalline double sulphate which is relatively coarse, and is easily filtered and washed free of zinc-bearing solution. Calcine is used to neutralise the acid that is liberated during precipitation of the iron. Also included in the Risdon plant are a separate stage for oxidation of ferrous iron by injection of air, and a pre-neutralisation stage, using recycled oxidation stage pulp, to neutralise excess acidity from the leaching stage before the jarosite precipitation stage. The residue treatment plant consists of conventional equipment such as covered agitated vessels, thickeners and filters. Operation will be continuous and product solution will join the main zinc plant circuit for further purifications and electrolysis. Marketable zinc production will be increased by 70 tonne per operating day by the treatment of residue.

Jan 1, 1970

By Alfred H. Bell, Virginia Kline

In 1944, Illinois produced 77,413,000 bbl. of oil, or 4.6 per cent of the total for the United States, and continued to rank sixth in the nation in oil production. This represents a decrease of 6 per cent from 1943, when- the total Illinois production was 82,256,000 bbl. This decrease was much less than the 23 per cent decrease in 1943 from production of the previous year. The principal factor in arresting the production declinc, which had been going on since 1941, seems to be the increased drilling that followed the relaxing of the Federal Government's rules in regard to well spacing. The daily average production for 1944 was approximately 212,000 bbl. Daily averages by months were as follows: Jan......... 219,000 July........ 206,000 Feb......... 220,000 Aug......... 211,000 Mar........ 216,000 Sept......... 209,000 Apr......... 211,000 Oct......... 210,000 May........ 213,000 Nov........ 209,000 June........ 209,000 Dec......... 205,000 During the year, 1991 wells were drilled for oil and gas in Illinois as compared with 1791 in 1943, an increase of II per cent. Of the 1991 wells, 430 are classified as "wildcat" as compared with 461 in 1943. Twenty-eight new pools (Table 2 A) were discovered in 1944 as compared with 29 in 1943. Changes in federal drilling regulations, permitting closer spacing of wells, resulted in a drilling program that emphasized development of proved acreage rather than wildcatting. Data on production and drilling by fields are given in Table I; data on annual production and drilling for Illinois, in Table 3. Discoveries Twenty-eight new fields (Table 2 A), 42 extensions (Table 2 B), and 39 additional producing zones in existing fields (Table 2 C) were discovered in 16 counties in Illinois during 1944. Of the 28 new fields, one was abandoned during the year, 14 were one-well fields, eight others had not more than 6 wells, one had 8, one had 9, one had 11, one had 15, and the largest new field, Roaches North, had 28 producing wells at the end of the year. In all, 109 wells were producing in these new fields on Jan. 2, 1945, as compared with 111 wells producing from 29 new fields at the end of 1943. . The average initial production of the discovery wells of the 28 new fields was 129 bbl. of oil and II bbl. of water, a notable decline from the average initial production of 194 bbl, of oil and 15 bbl. of salt water for the 1943 discovery wells. In fields discovered since 1936, the total number of oil wells producing at the end of 1944 was 12,335. Productive Acreage The area of proved production in the new fields (discovered since 1936) increased from 144,335 acres at the end of 1943 to 173,485 acres at the end of 1944 (Table I), an increase of 29,150 acres. Of this increased area, 1720 acres are in fields discovered during 1944 and 27,430 acres are in extensions of fields discovered earlier.

Jan 1, 1945

By L. R. Woodyatt, H. J. Beattie, C. T. Sims

Theories correlating the formation of u and related intermetallic compounds to the electron-per-atom density of binary and ternary alloys have appeared regularly in recent technical literature. These same principles can be modified and applied to complex precipitation-strengthened alloys such as the iron-, cobalt-, and nickel-base superalloys and the stainless steels. Since these complex alloys contain carbides and other phases that normally precipitate before the U-type phases, the nature and amount of the precipitated phases must be calculated first. The following general formula is then applied to the residual matrix composition of the alloy: element. The magnitude of the resulting number is indicative of whether the alloy will form a a -type phase. When these calculations (which are computerized) are systematically applied to alloys of knoun phase analysis, a breakoff in average electron-vacancy number is noted between U-free and U-prone alloys. Alloys with an average electron-vacancy number higher than the breakoff form a-type phases, while those with lower ones do not form these phases. This method could then be used to eliminate from consideration all experimental compositions that would precipitate undesirable phases. It also is useful in evaluating analyzed heats of alloys where minor heat-to-heat variations determine whether the alloy is o-free or o-prone. THE highly significant development of strong, ductile superalloys to provide reliable construction materials in the 1000" to 2500° F temperature range has been due principally to unremitting application of Edisonian techniques and logic by the dedicated physical metallurgists who have shouldered this responsibility. Tools such as the electron microscope, phase analysis, and computers to accomplish regression analyses have been used heavily, but the effort has been essentially practice of an art, rather than a science. The objective of this paper is to describe and illustrate application of some relatively fundamental principles to certain of these alloy systems in an attempt to remove some of the empiricism from the technology. Specifically, the work presented here deals with the use of periodic-group relationships to predict the formation of intermetallic phases which can occur in primarily austenitic (fcc) structures. Calculations that have been developed might be applied in the design of new alloys and the evaluation of known alloys, and thus have the potential of eliminating vast areas of unnecessary alloy preparation and evaluation. ALLOYING CONCEPTS AND STRUCTURAL FEATURES OF SUPERALLOYS Strength is produced in austenitic superalloys by three principle mechanisms: 1) precipitation of y'; 2) formation of carbides; 3) solid-solution hardening by soluble refractory metals. The first mechanism requires the addition of aluminum and titanium, the second requires carbon and carbide-forming elements, while the third calls for the addition of molybdenum and/or tungsten. A considerable concentration of chromium is usually maintained to resist oxidation/corrosion, but it is also an important carbide-forming element. Fig. 1 shows a sketch and electron micrograph of the structure of a typical wrought nickel-base super-

Jan 1, 1967

By H. D. Kynor

By the term mechanical mining is meant that operation, or series of operations, that replace the hand methods of mining. The first undercutting machine to operate in anthracite was placed in the Butler mine of the Hillside Coal and Iron Co., Dec. 23, 1910, by the Sullivan Machinery Co. The first Jackhamer used in the anthracite field was installed at the Wadesville colliery of the Philadelphia & Reading Coal and Iron Co. in Oct., 1912, by the Ingersoll-Rand Co. The first longwall conveyor was installed at the Dodge mines of the Delaware, Lackawanna, & Western Coal Co. in March, 1912. The first mechanical scraper equipment was installed in the Seneca mines of the Lehigh Valley Coal Co. in January, 1914. The amount of anthracite mechanically mined since the first mining machine was installed in 1910" is as follows: Penna. Coal Co. D. L. & W.. ScRanton Temple Hudson YeaR and Hill- Tons Coal Co., Coal Co., Coal Co., Total, side Coal Tons Tons Tons Tons and Iron. Tons 1920................ 372,737b 367,000d 322,892 74,127 371,878 1,508,634 1919................ 950,786 no record 306,616 81,575 319,356 1,658,333 1918................ 917,778 744,966 24,880 44,756 288,781 2,021,161 1917................ 757,940 838,800 5,050 57,279 164,180 1,823,249 1916................ 286,780 860,663 13,960 114,173 101,475 1,377,051 1915................ 428,819 592,169 8,253 1,029,241 1914................ 219,188 153,896 373,084 1913................ 171,505 1912................ 124,267 124,267 1911................ 40,319 40,319 1910................ 1,184 1,184 a A slightly greater production was obtained than here indicated, as the tonnage from individual operations is not shown. b Decrease due to strike conditions in 1920. c Does not include tonnage of D., L., & W. d D., L., & W. decrease in 1920 due to having fewer mining machines in operation. There are about 150 undercutters in use in the anthracite region, 80 mechanical loaders, and 10 longwall conveyors.

Jan 1, 1922

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations. Geology Composition and Morphology Diatomaceous silica qualifies as a. mineral of organic origin in much the same way that aragonite and collophane do. The silica of the fossilized diatom skeleton closely resembles opal or hydrous silica in composition (SiO2 • nH2O) .4, 12, 203 The silica is of acute biological significance, not only for the cell wall component, but also for the basic life process.45, 51 Without silica, cell development ceases .31 In addition to bound water, varying between 3.5 and 8%, the siliceous skeleton may also contain, in solid solution, or as part of the Si02 complex, small amounts of associated inorganic components-alumina, principally-and lesser amounts of iron, 46, 49, 55 alkaline earths, alkali metals, and other minor constituents.59, 63, 67 Boron is reported to be an essential element for diatom growth .52, 58 Since diatomaceous silica is not pure hydrous silica but contains other intimately associated elements, there is good reason to consider it a distinct type or variety.4 Associated with the diatomaceous silica, and integrated as part of the diatomite, may be variable amounts of organic matter, soluble salts, and particles of rock-forming minerals that were syngenetically deposited or precipitated with the diatom frustules. Sand, clay, carbonate, and volcanic ash are typical common contaminants. Other contaminating minerals may be present, such as feldspar, mica, amphiboles, pyroxenes, rutile, zircon-the result of weathering, then transporting, and subsequent redeposition of surrounding land masses. Commercial diatomite may also contain fragments and particles of

Jan 1, 1983

By Bauer, Alan

In considering blasting it is necessary to consider the drilling and explosives since one is generally concerned with the total cost of muck of a certain size in the pit or through the crusher. To get a current idea of the drilling situation in open pit mines plotted in Fig. 1 are the drilling costs per ton of material vs. hole diameter for rotary drill holes in large limestone, iron ore and taconite operations. The exception is the 2-in. diam hole which was drilled with a percussion drill in limestone.

Jan 1, 1968

By Leon Eliel

TEN years ago .a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these. isolated bits of infor-mation can be ascertained, the message begins to take meaning.. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

By A. Brown

RAPIDLY rising world demand for mineral products has accelerated depletion of the more readily accessible ores, particularly those of premium grade. Operations must proceed at a faster rate to deeper horizons, where there are problems of ground control that restrict economic recovery of the mineral and introduce new hazards to mine personnel. For some of the new Canadian mining fields severe problems of ground stress are still in the future, but much of Canada's mineral output comes from well established mines that have reached considerable depths. It must also be anticipated that the depletion of premium grade ores will eventually necessitate mining low grade material at competitive cost, and unsolved problems of ground control can materially increase costs. Studies of ground stress phenomena in underground workings are therefore considered a present-day necessity, especially since these investigations must be a long-term effort owing to the highly complex nature of the problem and the difficulty of making full-scale observations. In recent years the Mines Branch of the Department of Mines and Technical Surveys in Canada has conducted such an investigation. This report of the work is primarily concerned with stress problems in some Canadian coal mines and, in particular, with mine bumps. Mines Branch investigations of this and related problems are carried out by a small team of mining engineers and physicists who, with assistance from geologists, pool their special skills in an integrated program. These Canadian investigations combine a field and laboratory approach. Since data obtained under contrasting mining conditions allow useful comparisons of ground behavior under stress, this article will present data gathered under a wide range of Canadian coal mining conditions. Two contrasting longwalls in eastern Canada will be discussed and two dissimilar pillar extraction operations in western Canada. Locale of Observations In eastern Canada observations are being made in the collieries at Springhill, Nova Scotia. The district's No. 2 mine, which has a history of bump occurrences dating back to 1917, is currently being worked at a depth of 4200 ft. The mining method is longwall retreating along the strike and the practice is to retreat three walls in line, each about 350 ft long. There is no machine cutting or shooting—the coal is hand-picked and hand-loaded onto face conveyors. There are three rows of hardwood chock block supports parallel to the coal face. These supports are built during the two daily coal loading shifts, and the rear line is withdrawn during the midnight shift. The goaves are partially packed by stone midwalls 12 ft wide which are built forward daily in step with the face advance. The seam dips at 15° and averages 9 ft of strong, well cleated bituminous coal enclosed in competent beds of shales, sandy shales, and sandstones of Carboniferous age. The bumps rarely disturb the retreating longwall faces but manifest themselves as violent upthrusts of pavement in the levels leading to the walls. Observations have also been made in Springhill's No. 6 mine, which operated in a 5-ft seam of coal at a depth of about 2500 ft. Although No. 6 mine was

Jan 1, 1959

By R. A. Salathiel, A. D. Kaiser, P. H. Monaghan, B. E. Morgan

The productivities of many hydrocarbon-bearing for-rnntions appear to be reduced during drilling, completing and repairing operations. The reason for these othcarwise unexplainable low productivities may be a drastic reduction of formation permeability immediately surrounding the borehole. A possible cause of the reduced permeability is swelling and dispersion of clays present in porous media when contacted by fresh water or mud filtrates. Hence, the invasion of fresh water or mud filtrate into hydrocarbon-bearing formations that contain clays may cause low productivities as a result of formation damage. Present laboratory investigations have yielded results which supplement existing literature on formation damage. An expanded-type clay, montmorillonite, way found in hydrocarbon-bearing formations not previously analyzed. When sand columns and formation cores containing montmorillonite were contacted by fresh water, their oil permeabilities were reduced. This reduction in oil permeability way restored partially but not completely by a repair procedure, i.e., flooding with kerosene containing organic agents or flooding with water containing electrolytes. Hence, where montmorillonite is present in formations, prevention of formation danzage was indicated to be the only complete solution to the problem. To prevernt formation damage, results suggested use of an approximately 1 per cent solution of calcium chloride or stronger solutions of sodium or potassium chloride. In conventional rotary drilling operations the wall of the hole is exposed to drilling mud for days, weeks, and in some instances for as long as several months. During this time, drilling mud filtrate seeps slowly into formations surrounding the hole. The permeability and stability of many formations, especially those containing clayey materials, are impaired by the mud filtrate. Often interaction between the mud filtrate and the formation causes drilling and production difficulties. Serious reduction in productivity of oil and gas formations during drilling, completing and repairing wells has been noted often in recent years. Cases are known of development wells which produced only small volumes of fluid upon completion. However, after a period had elapsed, they began to produce oil or gas in commercial quantities. In other cases, results of drill-stem tests taken during the drilling of deep wells have indicated good production should be obtained from shallow formations. Later difficulty has been experienced in obtaining production from these shallow formations which had remained in contact with drilling muds for an extended time. In yet other cases wells have failed to attain the productivities expected from previous performance after the use of drilling mud as a circulating fluid during workover operations. It is evident from the field behavior cited that the productivities of certain oil- and gas-bearing formations have been damaged by exposure to drilling muds. This reduction in well productivity, called "formation damage", causes serious consequences. In development wells, expensive remedial operations are incurred. In wildcat wells, good formations may appear to be marginal or even non-productive. The importance of formation damage has been recognized by a number of investigators1-s who have considered the effects of fresh water, saline solutions and aqueous mud filtrates on the permeabilities of formations. A general conclusion from such studies is that interaction between water and formation clays reduces permeability of reservoir rock and that the permeability decreases as salinity of the water decreases. Data in these references, however, concern the permeability change with only a single fluid present. A more pertinent and direct consideration in the production of oil and gas from wells is the permeability change when two fluids, oil and water, are present. Recognizing this, Nowak and Kreuger2 and Bertness1" considered several ways in which mud filtrates and saline solutions caused reductions in the oil permeability of formation cores. Investigations discussed here were designed to supplement information in the literature on changes in oil

By I. M. Roberts

THE war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-furnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to. meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19 ¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. COKING CHARACTERISTICS OF COALS Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

By P. Gobin, J. Perez, P. Peguin

The strain-amplitude- dependent part of the internal friction of alluminum after several ther momechanical treatments has been measured in the I-cycle range and at the ambient temperature. The internal friction in the outer layer of the torsional specimen us stress is computed from the experimental data. The curues obtained are analyzed in tevnzs of u coirzbinntion of AH and p, which aye, respectively, due to the vecersible unpinning from weak pills and to the plastic strain. Considerirlg the notion of thermally activated unpinning and repinning, it is shown that in our experimental conditions tlze dislocation lines acl as in the H model of Granato and Liiclze. It is also seen that the internal friction p which appears at higher- strains call be described by a simple expression which is in good agreement with our results. A qualitative interpretatiorz is proposed by combining these new types of intelpnal fviction. We define the internal friction 6 as half the ratio of the dissipated energy aW during one cycle to the maximum supplied strain energy W of a material submitted to a periodic stress. Experiment and theory show that internal friction varies with stress above a critical value.' Below this value the internal friction is strain-amplitude-independent and is often masked by an experimental background; so we shall call it AB. ~bove this critical value, the internal friction is strain-amplitude-dependent. This quantity is usually called aH:' and it can be explained as a thermal unpinning of dislocations.3-6 Furthermore, at higher stresses, a rapid increase of internal friction appears. This phenomenon could be caused by the plastic strain,' so we shall call it Ap. It seems interesting to us to study the influence of several t her momechanical treatments on the curve internal friction 6 vs strain E, in order to study the variation of AH and p with the concentration and the repartition of linear and point defects. In order to try to explain the results obtained, we shall propose and discuss models for H and hp and shall show that we obtain a combination of these two types of internal friction. 1) EXPERIMENTAL PROCEDURE 1) Preparation and Treatment of Specimens. We

Jan 1, 1968

By C. W. Macgregor

The observation of the flow layers, or Luders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-st'eel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are ill reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45" to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ncr, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45" to the principal stress direct-tions at the point. As examples of the latter may be mentionecl the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subject,ed to internal pressure only, etc. IIencc if the flow layers are observed from an experiment, the shear-st'ress trajectories —the curves indicating the direct,ions of the maximum shearing stresses in the body—may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45" to the principal stress directions, the family of principal stress trajectories, or the curves irldicating the directions of the principal stresses, may be thus obtained Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowai~; in duralumin and other aluminum alloys, by Dawidenkow,~Elam,~ Fell4 an(l others; in copper and copper-alloy crystals, by Elam;~ in brass by Elam;3 in brass wires by deForest;" in higher carbon steels, tungsten steel, and

Jan 1, 1939

By R. J. S. Brown, B. W. Ganison

A new logging method has been developed, based on measurement of the nuclear magnetism of formation fluids. The nuclear magnetism log (NML) is the only log that responds solely to formation fluids. It operates equally well in both oil-base and water-base muds and in empty holes, and can be used in all kinds of formations except strongly magnetic ones. Two separate NML measurements can be made, one of which provides a continuous formation fluid curve. This fluid curve is called the free fluid log (FFL) and is believed to indicate a minimum effective porosity in most formations. The FFL not only delineates fluid-containing zones, but provides an excellent correlation curve that can be obtained under conditions where conventional correlation logs are ineffective. Preliminary tests indicate that the second kind of NML measurement may help distinguish oil and water zones and provide information concerning permeability and wettability. (The FFL itself appears to provide some information on permeability.) The second kind of NML measurement requires stopping the logging tool for a short time opposite a zone of interest and taking more extensive NML data that can be displayed as nuclear magnetic relaxation curves. In some instances, oil and water saturations for the region immediately adjacent to the borehole can be read from these relaxation curves. INTRODUCTION In 1946, Bloch, Hansen and Packard and Purcell, Torrey and Pound3 independently announced the successful demonstration of the phenomenon of nuclear magnetic resonance. During the past 13 years, there have been many applications of nuclear magnetic resonance, including applications to the study of chemical structure and to the measurement of magnetic field strengths. Preliminary experiments on the feasibility of using nuclear magnetism measurements in well logging were made independently by California Research Corp. and Varian Assoc., the Varian work being sponsored by the Byron Jackson Tools, Inc. Since then a cooperative research program on nuclear magnetism logging has been carried out by the Byron Jackson Div. and Research Center of Borg-Warner Corp., and California Research Corp., subsidiary of Standard Oil Co. of California. The use of nuclear magnetism in well logging is of special interest because it offers a way of making direct measurements on the hydrogen in the formation fluids and not on the rock matrix. Within the past 1 1/2 years, successful measurements have been made with a research model logging tool in wells in California, Tex as, Utah, Louisiana and Wyoming. NUCLEAR MAGNETISM SIGNALS Polarization, Relaxation and Precession Many atomic nuclei possess magnetic moments and spins; that is, they are similar in some respects to bar-magnet and gyroscope combinations. Molecules and their nuclei are subject to thermal motion, which has a scrambling effect, tending to leave as many nuclear spins oriented in any one direction as in any other. However, if a magnetic field is applied, the magnetic nuclei tend to align in the direction of the field. The scrambling and aligning forces compete with each other, with the result that a few more spins are oriented parallel to the field than in other directions. This gives a net magnetization, or polarization, which is directly proportional to the strength of the applied magnetic field (aligning influence) and inversely proportional to the absolute temperature (scrambling influence). When the magnetic field in, or temperature of, a liquid sample containing protons is changed, the new equilibrium value of proton polarization is not established immediately but requires an amount of time which depends on the nature of the hydrogen-containing materials. The process of approaching the equilibrium value of polarization is called relaxation.'.' Polarization is a vector quantity, and the components parallel to and perpendicular to the magnetic field must be considered separately. Relaxation of the component parallel to the field is called "thermal relaxation", or "longitudinal relaxation", and the corresponding time for this component of non-equilibrium polarization to decay by a factor of e (natural log base) is denoted T. The relaxation of the perpendicular component is called "transverse relaxation", and the corresponding relaxation time is denoted T,. The potential energy of a magnet in a uniform field depends on the angle the magnet makes with the field; therefore, a change of the component of net polarization parallel to the magnetic field involves an exchange of energy between the spin system and the thermal motion of the molecules, leading to the term thermal relaxation for the relaxation of this component. Suppose we subject a sample to a strong magnetic field at right angles to the earth's field for a time greater than TI. A polarization, thus, is established at right an-

By A. L. Benham, W. E. Dowden, W. J. Kunzman

The mechanism involved in creating a miscible fluid displacement of typical reservoir fluids through porous media by light hydrocarbon mixtures usually involves a number of mixing and separation stages in the contact area. This mechanism has been illustrated on ternary diagrams for miscible displacement of reservoir fluid by rich hydrocarbon gases. A relatively simple method has been devised for calculating the approximate conditions for a miscible displacement of reservoir fluid by rich, light hydrocarbon gases or by LPG mixtures. Miscibility is favored by increased pressures, decreased temperatures, light reservoir fluids and light hydrocarbon-displacing fluids rich in the heavier components. The conditions for miscible displacements of five typical reservoir fluids by various light hydrocarbon mixtures were determined for a range of temperatures from 70" to 260°F and pressures from 1,000 to 3,000 psia. A correlation of these conditions was obtained using the variables of temperature, pressure, C,+ molecular weight of the reservoir fluid, C,+ molecular weight of the displacing fluid, and mol per cent methane in the displacing fluid. This correlation has been applied to data appearing in the literature with very good success. A partial check of the correlation has been made using a step-wise procedure with a windowed PVT cell. INTRODUCTION The term, "miscible fluid displacement", may be defined as any oil-recovery displacement process where there is an absence of a phase boundary or interface between the displaced and displacing fluids. A water flood would not be a miscible fluid displacement, although cycling in a condensate reservoir would be. Another example is displacement of oil by gasoline. Not so obvious, however, are the conditions under which fluids (such as propane, mixtures of propane and methane, or other similar systems) will give a miscible fluid displacement of oil. There are four standard miscible-fluid-displacement processes being used for the recovery of oil from an "nderground reservoir—(1) high-pressure dry-gas miscible displacement, (2) rich-gas miscible displacement, (3) miscible slug using a slug of LPG followed by a lean dry gas under miscible conditions, and (4) gas driven-slug process using a slug of LPG followed by a lean dry gas under immiscible conditions. The first problem faced by the engineer designing a miscible displacement process is to determine the conditions for miscibility. A number of papers have included discussions of the process of obtaining miscibility in these processes.1-8 However, methods for calculating the conditions for miscibility have not been published. This paper includes a method for calculating the conditions for a miscible displacement of reservoir fluid by a rich gas (LPG diluted with methane or natural gas). In this paper, a rich-gas miscible displacement process is defined as an oil-recovery process in the reservoir. The cost of a rich-gas miscible displacement will be decreased by diluting the LPG with methane or natural gas as much as possible. Therefore, it is important to be able to predict the maximum dilution for miscibility. MECHANISMS The mechanisms for obtaining miscibility between a displacing mixture of light hydrocarbons and displaced reservoir fluid often involve a number of displacing and mixing stages. As stated previously, the cost of a rich-gas miscible displacement is decreased by diluting available LPG with natural gas. The problem is to predict the maximum dilution allowed while maintaining miscibility. To get a picture of the displacing and mixing stages, it is helpful to consider these complex hydrocarbon mixtures as pseu do-ternary systems. Graphical representation of a complex system as a pseu do-ternary system can be thermodynamically rigorous if enough variables are used to describe the character of each pseudo-component in one of the phases. However, even if the characterization of each pseudo-component is not complete, pseudo-ternary representation does serve to illustrate the mechanism for obtaining miscibility and can be used to make some general conclusions concerning the conditions for obtaining miscibility. A phase diagram for the ternary system, methane-

By C. W. MacGregor

The observation of the flow layers, or Luders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-st'eel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are ill reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45" to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ncr, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45" to the principal stress direct-tions at the point. As examples of the latter may be mentionecl the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subject,ed to internal pressure only, etc. IIencc if the flow layers are observed from an experiment, the shear-st'ress trajectories —the curves indicating the direct,ions of the maximum shearing stresses in the body—may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45" to the principal stress directions, the family of principal stress trajectories, or the curves irldicating the directions of the principal stresses, may be thus obtained Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowai~; in duralumin and other aluminum alloys, by Dawidenkow,~Elam,~ Fell4 an(l others; in copper and copper-alloy crystals, by Elam;~ in brass by Elam;3 in brass wires by deForest;" in higher carbon steels, tungsten steel, and

Jan 1, 1939

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.' : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*'" Exotic recovery processes have been considered primarily for ' perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969